JP5846980B2 - Dental adhesive kit - Google Patents

Description

  The present invention relates to a dental adhesive kit used for restoration of teeth in the field of dentistry and the like.

  For the restoration of teeth damaged by caries or the like, a filling material called a composite resin is mainly used. This composite resin is generally used after being filled in a cavity of a tooth and then cured by polymerization. However, since the composite resin itself does not have adhesiveness to a tooth, such as enamel or dentin, it is necessary to use it together with a dental adhesive using a polymerizable composition. Therefore, such an adhesive is required to adhere to both the composite resin and the dentin.

Conventionally, in order to improve the adhesive strength of the adhesive to the tooth,
(A) Etching treatment of hard teeth (mainly enamel),
(B) a priming treatment in which an adhesion-improving component called a primer is infiltrated into the tooth structure;
The pre-processing was performed.

  The etching treatment is a treatment for demineralizing the tooth using an acid aqueous solution, and the surface of the tooth demineralized by the acid exposes the rough enamel and dentin. After the etching process, the adhesion mechanism of the adhesive to the exposed enamel and dentin is different, and is specifically as follows.

Adhesion of the adhesive to the enamel is achieved by a macro mechanical fit in which the adhesive component penetrates and cures to the rough surface deashed with the acid aqueous solution. On the other hand, the adhesive is bonded to the dentin by a micro mechanical fit in which the adhesive composition penetrates into the fine voids of the sponge-like collagen fibers exposed on the surface of the dentin after decalcification and hardens. This is achieved by the combination.
However, it is not easy to infiltrate the adhesive composition into the fine voids of the collagen fiber. For this reason, after the decalcification treatment, further penetration (priming treatment) of the primer into the dentin (especially dentin) is performed. After that, the adhesive is applied.

  As described above, in order to obtain good adhesion strength to both enamel and dentin, two stages of pretreatment, etching treatment and priming treatment, are performed when repairing damaged teeth, A three-step system in which the two-stage pretreatment is performed and then the adhesive composition is applied to the tooth surface and cured (bonding treatment) is a basic means, and is called a total etching treatment method.

  The pre-processing by the total etching process of the three-step system currently being implemented includes a method called wet bonding in which the priming process and the bonding process are performed separately, and a method called self-etching in which the etching process and the priming process are performed in one liquid. There are both advantages and disadvantages.

  In general, wet bonding is performed by applying a relatively strong acid (for example, phosphoric acid) to the tooth surface to be treated as an etching material and performing an etching process, and then applying a permeable adhesive composition to perform a priming process. That's it. In this case, when a polymerizable composition containing a photopolymerization initiator is used as the permeable adhesive composition, the adhesive composition is used as an adhesive (bonding material) for joining the composite resin. Since it functions, a bonding process can also be performed by polymerizing and curing by light irradiation following the priming process.

  In such a method, since the etching process is performed using a relatively strong acid, the roughening of the enamel proceeds effectively, and therefore the mechanical fitting force with the enamel can be increased. That is, wet bonding is advantageous in improving the adhesive strength with the enamel.

However, after the etching process, it is necessary to remove the etching material by washing with water, and at the same time, the tooth surface exposed by the etching is kept wet, and a permeable adhesive composition is not applied in this state. Don't be. That is, if the etching material remains, the enamel roughening progresses excessively and the cavity becomes large, so this etching material must be removed. Also, if the tooth surface exposed after the etching process is dried, the collagen fibers forming the dentin shrink and the penetration of the adhesive composition becomes difficult. It is necessary to keep it.
As can be understood from this, wet bonding has a drawback that it is difficult to ensure adhesion to dentin (high technique sensitivity). This is because the penetration degree of the adhesive composition varies depending on the wetness of the tooth surface after the etching treatment, which greatly affects the adhesion to dentin. Moreover, since the adhesiveness with respect to dentin becomes unsatisfactory, there also exists a problem that adhesive durability is also low.

  On the other hand, in self-etching, the etching process and the priming process are performed in one solution, so the number of processes is smaller than in wet bonding, and the etching material is removed during the priming process or the tooth surface is wetted. Naturally, it is a great advantage that a troublesome operation such as holding is not necessary, and high adhesiveness can be obtained stably especially for dentin.

  However, self-etching has a problem that adhesion to enamel is insufficient. That is, since the etching process and the priming process are performed with the same liquid, it is necessary to control the storage stability of the liquid and the degree of the etching process to some extent, so that a strong acid cannot be used. When a strong acid is used as an etching material, the solution is gelled, and the etching processing ability and permeability are impaired. In addition, erosion of enamel as well as dentin proceeds greatly, and a large cavity is formed. Therefore, it is unavoidable to use a weak acid as an etching treatment material, and therefore the enamel roughening does not proceed sufficiently, resulting in insufficient mechanical fitting force to the enamel, and the enamel Adhesiveness with respect to is insufficient.

  Thus, both wet bonding and self-etching are unsatisfactory in adhesion to either enamel or dentin. At present, various dental adhesive compositions have been proposed, but it can be said that few exhibit excellent adhesion to both enamel and dentin. Even if there are those that show adhesion to both enamel and dentin, there is still a need for improvement in adhesion to either enamel or dentin.

  For example, Patent Document 1 proposes a dental adhesive composition containing a polymerizable monomer and a titanium compound having an alkoxy group, but such a composition has good adhesion to dentin. Can't get. For example, by applying this adhesive composition to the tooth surface after an etching treatment using an etching material and then performing polymerization and curing, it is possible to ensure good adhesiveness to enamel, but to dentin Adhesion is not sufficient. This is also clear from the fact that Patent Document 1 does not even evaluate the adhesive strength to dentin.

  Patent Document 2 discloses a one-component adhesive composition containing a Group 4 element ion together with a polymerizable monomer in order to improve adhesive strength and durability. This one-component adhesive composition performs etching and priming by self-etching, and since it is a weak acid, it is required to further improve the adhesion to enamel.

  Furthermore, Patent Document 3 discloses an adhesive composition that can provide excellent wetting characteristics of a tooth surface even when the tooth surface is excessively dried by using a specific monomer. . The adhesive composition is capable of exhibiting stable adhesion even when the dentin etched with phosphoric acid is dried, but the adhesion strength to the dentin is not yet sufficient and the durability is also low. Therefore, further technical improvements are expected.

JP 56-136865 A WO2010 / 010901 Special table 2009-542740

  Accordingly, an object of the present invention is to provide a dental adhesive kit including an adhesive composition that can form a cured product that exhibits high adhesive strength to both enamel and dentin and has excellent adhesion durability. It is to provide.

  Conventionally, in a composition in which a group 4 ion coexists with an acidic group-containing polymerizable monomer, ionic crosslinking is formed in the polymerized cured product, thereby improving the adhesion of the cured product to the tooth. However, among the group 4 ions, the present inventors have particularly high affinity for titanium (IV) ions not only for ion cross-linking but also for collagen forming dentin. As a result, the present inventors have found that such a monomer component containing titanium ions can easily penetrate into dentin, and have completed the present invention.

According to the present invention, in a dental adhesive kit including a package (A) containing a phosphoric acid etching material and a package (B) containing an adhesive composition,
The adhesive composition is
(A) a polymerizable monomer component containing an acidic group-containing polymerizable monomer (a1); and
(B) Titanium (IV) ions;
(C) solvent;
A dental adhesive kit characterized in that it is included is provided.

The dental adhesive kit of the present invention is
(1) The titanium (IV) ion (b) is 1 g of the acidic group-containing polymerizable monomer (a1).
Present in the adhesive composition in an amount of 0.2 to 1.5 moles per
(2) The polymerizable monomer component (a) has a hydrogen phosphate diester group,
(3) the solvent (c) is water, a water-soluble organic solvent or a mixed solvent thereof;
(4) The adhesive composition contains a polymerization initiator (d),
(5) The adhesive composition contains 1 mol of titanium (IV) ion (b),
Containing 0.4 to 2.0 moles of fluoride ions (e),
Is preferred.

The dental adhesive kit of the present invention includes a package (A) containing a phosphoric acid etching material and a package (B) containing an adhesive composition, and is understood from the structure of such a package. Thus, in this dental adhesive kit, after the etching process is performed using the phosphoric acid etching material, the priming process using the adhesive composition is performed.
Therefore, in the present invention, the etching process is performed using phosphoric acid, which is a relatively strong acid. For this reason, the enamel of the tooth can be roughened, the mechanical fitting force between the cured product and the enamel can be improved, and the adhesion of the cured product to the enamel can be improved.

  In the dental adhesive kit of the present invention, the priming treatment is performed using the adhesive composition contained in the package (B). The titanium (IV) ions (b) present in the composition are used. In addition to forming a cross-linked structure, the composition rapidly penetrates into the dentin exposed by the etching treatment, so that a cured product with further improved adhesion to the dentin can be formed.

In the present invention, the penetration of the adhesive composition into the dentin is estimated from the experimental results of Examples described later by the present inventors.
That is, in addition to the fact that the cured product exhibits high adhesive strength to dentin and the durability of the cured product to the dentine is high, the priming treatment using this adhesive composition is performed after the etching treatment. Even when the tooth surface is dried, a high adhesive strength close to that obtained when the tooth surface is wet is obtained. However, when the tooth surface is dry, the collagen fibers forming the dentin are in a contracted state, and the adhesive composition should be extremely difficult to penetrate. Therefore, even when the collagen fiber is in a contracted state, an adhesive strength close to that when the collagen fiber is not contracted (the tooth surface is wet) can be obtained. This is considered to be due to the fact that this composition rapidly penetrated into the contracted collagen fibers.

  In addition, even when the tooth surface after the etching treatment is performed in a dry state, it is possible to obtain a high adhesive strength close to that obtained when the tooth surface is wet. This means that no technique sensitivity is required, which is also a great advantage of the present invention.

  The dental adhesive kit of the present invention includes a package (A) containing a phosphoric acid etching material used for an etching process and a package (B) containing an adhesive composition used for a priming process. Is included.

<Package (A)>
As described above, the phosphoric acid etching material accommodated in the package (A) etches the tooth surface to decalcify the enamel on the tooth surface, thereby making the surface rough and rough. In addition, the mechanical fitting force between the cured product and enamel formed in this portion is increased, and the adhesive strength between the two is improved.

Such a phosphoric acid etching material is known per se and is an aqueous solution of orthophosphoric acid (H ₃ PO ₄ ).
It should be noted that acids other than phosphoric acid cannot be used because they have problems with compatibility with living bodies or etching ability with respect to tooth structure. For example, with citric acid, the decalcification power becomes insufficient and the adhesion strength to the enamel is lowered.

  The phosphoric acid concentration of the phosphoric acid aqueous solution should just be set to the extent which shows the moderate etching effect (decalcification power), without giving a bad influence in an oral cavity, Generally 30-50 mass%, Especially 35-35 mass%. It is about 45% by mass. For example, if the phosphoric acid concentration is too high, the oral cavity may be adversely affected, and if the phosphoric acid concentration is too high or too low, the deashing power tends to decrease.

  In addition to the phosphoric acid etching material, the package (A) may contain various additives that can be used for the etching process in amounts that do not adversely affect the etching process. For example, a pigment as disclosed in JP-A-2005-8537 can be blended in an amount of about 10 to 1000 ppm in order to achieve a degree of decalcification. In addition, in order to increase the viscosity of the phosphoric acid etching material so that an appropriate amount can be applied to a predetermined cavity, inorganic fine particles, water-soluble polymers, etc. can be blended in an amount of about several percent. Etc. can also be mix | blended suitably.

The etching process using such a phosphoric acid etching material is performed by applying the etching material to the tooth surface to be repaired using a small brush or the like, and the processing time is the cavity formed on the tooth surface. Generally, it is about 10 to 30 seconds, though it varies depending on the degree of.
After this etching process is completed, this tooth surface is washed with water to remove phosphoric acid etching material and decalcified material generated by etching, and then priming with the adhesive composition contained in the package (B) Processing is performed.

<Package (B)>
The adhesive composition contained in the package (B) used for the priming treatment contains a polymerizable monomer component (a), and further, titanium (IV) ions are contained in this composition. (B) is present, and further includes a solvent (c) for allowing ions to be present, and a polymerization initiator (d) and fluoride ion (e) can be blended as necessary.

  The priming treatment using such an adhesive composition is usually performed by applying the adhesive composition as it is to a tooth surface in which the phosphoric acid etching material is removed by washing with water and is in a wet state. However, it is also possible to perform the priming process by applying this adhesive composition after the moisture is removed by air blow or the like to dry the tooth surface. That is, even when the tooth surface is dried and the collagen fibers are contracted, it is possible to ensure an adhesive strength equivalent to or close to that in a wet state where the collagen fibers are not contracted. Thus, the present invention has the advantage that high technique sensitivity is not required for dentin bonding.

In addition, the adhesive composition used for the priming treatment of such a tooth is a tooth surface as a primer for firmly adhering and holding a dental adhesive for adhering and fixing an orthodontic bracket and a composite resin. The adhesive composition itself can be used as a dental adhesive or as a primer for a composite resin.
Hereinafter, each component mix | blended with this adhesive composition is demonstrated.

[Polymerizable monomer component (a)]
The polymerizable monomer component (a) (hereinafter simply referred to as “monomer component”) in the adhesive composition is a variety of materials (for example, orthodontic brackets) applied on the adhesive composition. , Composite resin, dental adhesive, etc.).

  In order to sufficiently exhibit the ability of the adhesive composition to penetrate into the tooth structure and the ability to improve adhesiveness by ion crosslinking of tetravalent titanium ions described later, at least a part of the monomer component is an acidic group. It is necessary to be a containing polymer (a1), and a polymer (a2) having no acidic group is appropriately contained on the condition that the acidic group-containing polymer (a1) is present. . That is, if the acidic group-containing polymer (a1) is not included, it will be difficult to allow a sufficient amount of tetravalent titanium ions to be described later to be present in the adhesive composition. In addition, a sufficient ionic cross-linking structure is not formed in the cured product, resulting in unsatisfactory adhesion and adhesion durability to not only dentin but also enamel.

Acidic group-containing polymer (a1);
The proportion of the acidic group-containing polymer (a1) (hereinafter simply referred to as acidic monomer) occupying the monomer component (a) is generally 5% by mass or more, but the preferred content is that of the adhesive composition. It varies slightly depending on the usage pattern.
For example, when the adhesive composition of the package (B) is used as a mere dentin pretreatment material (that is, used only for priming treatment), 5 to 80 mass in the monomer component (a). %, Particularly 20 to 70% by mass, is the acidic monomer (a1). Further, when the adhesive composition itself is used as a dental adhesive, 5 to 50% by mass, particularly 10 to 30% by mass is preferably the acidic monomer (a1). Is a polymerizable monomer (a2) which does not contain an acidic group. In general, when used as a dental adhesive, a polymerizable monomer (a2) that does not contain an acidic group in order to give itself sufficient adhesiveness to a composite resin, an orthodontic bracket or the like. ) Is used more than when used as a dental pretreatment material.

  The acidic monomer (a1) described above is not particularly limited as long as it is a compound having at least one acidic group and at least one polymerizable unsaturated group in one molecule, and a known compound can be used.

  The acidic group (a1) in the molecule is not particularly limited as long as it does not adversely affect the human body, but in general, a carboxylic acid group (including an anhydride group) or a carboxylic group Suitable groups include acid groups and phosphoric acid groups (phosphoric acid-containing groups, phosphonic acid-containing groups, phosphinic acid-containing groups), and include phosphoric acid-based groups (-P (= O) (OH). Groups containing groups are preferred.

Specific examples of the phosphoric acid group are as follows.
Groups containing phosphate groups:
-OP (= O) (OH) ₂ ;
(—O—) ₂ P (═O) (OH);
Groups containing phosphonic acid groups:
-O-P (= O) R (OH)
-AP (= O) (OH) ₂ ;
Groups containing phosphinic acid:
-AP (= O) H (OH)
_{(-A-) 2 P (= O} ) (OH);
In the above, R is a hydrogen atom or an organic group, and A is an organic group.

In the present invention, among such phosphate groups, a group containing a phosphate group, particularly a group containing a hydrogen phosphate diester group [(—O—) ₂ P (═O) (OH)], It is most preferable from the viewpoint that ion cross-linking property by tetravalent titanium ions described later is most effectively exhibited, the bond strength to the tooth substance and the like is essentially increased, and particularly high adhesive strength can be obtained.

Examples of the polymerizable unsaturated group that the acidic monomer (a1) has in the molecule include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. Things can be mentioned.
In particular, from the viewpoint of curing speed, the acidic monomer (a1) is preferably a compound having an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group as a polymerizable unsaturated group.

The acidic monomer (a1) having an acidic group and a polymerizable unsaturated group in the molecule as described above can be used alone or in combination of two or more. Typical examples of the acidic monomer (a1) suitably used, for example, a polymerizable monomer containing a hydrogen phosphate diester group as an acidic group are as follows.
Bis [2- (meth) acryloyloxyethyl] hydrogen phosphate Bis [3- (meth) acryloyloxypropyl] hydrogen phosphate Bis [4- (meth) acryloyloxybutyl] hydrogen phosphate Bis [6- (meth) acryloyl Oxyhexyl] hydrogen phosphate bis [10- (meth) acryloyloxydecyl] hydrogen phosphate bis [12- (meth) acryloyl oxide decyl] hydrogen phosphate bis [2- (meth) acryloyloxypropyl] hydrogen phosphate bis [ 3- (Meth) acryloyloxypropan-2-yl] hydrogen phosphate bis [(meth) acryloyloxyethoxyethyl] hydrogen phosphate bis [(meth) [Chloroyloxydiethoxyethyl] hydrogen phosphate bis [(meth) acryloyloxypolyethoxyethoxyethyl] hydrogen phosphate 2- (meth) acryloyloxyethylphenyl hydrogen phosphate 2- (meth) acryloyloxyethyl ethyl hydrogen phosphate 2 -(Meth) acryloyloxyethyl butyl hydrogen phosphate

A polymerizable monomer not containing an acidic group (a2);
The polymerizable monomer (a2) that does not contain an acidic group that can be used in combination with the acidic monomer (a1) (hereinafter referred to as a non-acidic monomer) does not contain an acidic group and has at least one molecule in the molecule. As long as the condition that it has a polymerizable unsaturated group is satisfied, a known compound can be used without any limitation. Examples of the polymerizable unsaturated group possessed by such a polymerizable monomer include those similar to those exemplified for the acidic monomer (a1) described above, and in particular, an acryloyl group, a methacryloyl group, and an acrylamide group. A methacrylamide group is preferred.

  Typical examples of such a non-acidic monomer (a2) include the following (meth) acrylate monomers, and these can be used alone or in combination of two or more.

1. Mono (meth) acrylate monomers;
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 (meth) acrylate,
Glycidyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate,
Glyceryl mono (meth) acrylate,
2- (meth) acryloxyethyl acetyl acetate and the like.

2. Polyfunctional (meth) acrylate monomers;
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,
Epoxy (meth) acrylate and the like.

  Moreover, it is also possible to mix and use polymerizable monomers other than the (meth) acrylate monomers. Examples of such other polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; styrenes such as styrene, divinylbenzene, α-methylstyrene, and α-methylstyrene dimer. Compounds; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate; These other polymerizable monomers can be used alone or in admixture of two or more.

  In the present invention, when a highly hydrophobic polymerizable monomer is used as the non-acidic monomer (a2), parents such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are also used. It is preferred to use a volatile monomer. By using such an amphiphilic monomer in combination, it is possible to prevent separation of water, which is an essential component of the adhesive composition of the present invention, and to ensure the uniformity of the composition, and to stably provide high adhesive strength. It is because it can obtain.

[Titanium (IV) ion (b)]
In the present invention, the adhesive composition (B) needs to contain titanium (IV) ions (b).
That is, by allowing the tetravalent titanium ion (b) to be present in the adhesive composition, the permeability to the dentin can be greatly improved. As mentioned above, this titanium ion has a very high affinity for the dentin collagen fibers exposed by the etching process, and thus, for example, sufficiently penetrates into the gaps of the collagen fibers in a dried and contracted state. It will be. That is, the presence of the tetravalent titanium ion (b) significantly improves the priming ability of the adhesive composition.

  Further, as already known, the tetravalent titanium ion (b) forms a strong ionic bond with the acidic group in the polymerizable monomer component described above. That is, by polymerizing a composition containing such an ionic bond, ionic crosslinks of polymer chains are formed, and the effect of improving the adhesive force by ionic crosslinks is also exhibited. Therefore, the above-mentioned high penetrability into the dentin and ionic crosslinkability act synergistically, and the adhesion to the dentin such as enamel and dentin and the adhesion durability are remarkably improved.

  Of course, when it comes to ion cross-linking properties, it also contains polyvalent metal ions other than tetravalent titanium, such as zirconium ions, and therefore, adhesion to the tooth is also achieved by the presence of such polyvalent metal ions. Can be improved. However, such other polyvalent metal ions have poor affinity for collagen fibers and do not have satisfactory priming ability. In particular, the permeability to dry dentin is greatly reduced. Therefore, compared with the case where polyvalent metal ions other than tetravalent titanium are present, the effect of improving the adhesion is inferior.

  In the present invention, such a tetravalent titanium ion (b) is, for example, 0.2 to 1.5 mmol, particularly 0.4 to 1.2 mmol, per 1 g of the above-mentioned acidic monomer (a1). It is preferably present in the adhesive composition. That is, by the presence of tetravalent titanium ions at such a concentration, the permeability to dentin and the ion cross-linking property due to the cooperative action of the acidic monomer (a1) are effectively expressed, and the adhesiveness The improvement effect can be maximized.

The amount of tetravalent titanium ions present in the adhesive composition is determined by removing an inductively coupled plasma (ICP) emission analyzer or fluorescent X-ray (XRF) analyzer after removing solid components from the composition. It can be determined by measurement using.
For example, when using an ICP emission analyzer, 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 with a syringe filter or the like to remove solid components. The titanium ion concentration in the obtained filtrate can be measured with an ICP emission spectrometer, and the amount of tetravalent titanium ions present in the adhesive composition can be calculated.
Moreover, when using an XRF analyzer, an adhesive composition is filtered with a syringe filter etc. and a solid component is removed. The titanium ion concentration in the obtained filtrate can be measured with an XRF analyzer, and the amount of titanium ions present in the adhesive composition can be calculated.

  The amount of acidic groups in the adhesive composition is determined by isolating the acidic monomer (a1) from the composition by preparative high performance liquid chromatography and measuring the molecular weight by mass spectrometry of the isolated acidic monomer (a1). Further, the structure is determined by performing nuclear magnetic resonance spectroscopy (NMR) measurement. Further, using the isolated acidic monomer (a1), a calibration curve with a standard substance is prepared, and the standard substance is added to a part of the filtrate described above and measured by high performance liquid chromatography. The amount of monomer (a1) can be calculated.

  In the present invention, in order to adjust the amount of tetravalent titanium ions present in the adhesive composition within the above range, a titanium compound capable of releasing tetravalent titanium ions blended in the adhesive composition. May be set in accordance with the ion release properties.

  Examples of such ion-releasing titanium compounds include titanium alkoxides such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, zirconium methoxide, zirconium ethoxide, zirconium propoxide, and zirconium isopropoxide. Typical, titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, etc., elution of titanium ions is fast, and since the by-product is alcohol, the adhesive strength is not affected and the removal of the by-product is easy. It is preferable because it is easy to handle. In addition to titanium alkoxides, salts of titanium and various acids, titanium halides (especially fluorides), and the like can be used, and furthermore, titanium ion-releasing fillers can be used. The titanium alkoxide described above is most preferable in that titanium ions can be more stably released and the amount of titanium ions can be set with high accuracy.

[Solvent (c)]
The solvent is necessary for uniformly dispersing the above-described tetravalent titanium ions (b) and other components in the adhesive composition, and generally a water-soluble organic solvent or water is used as the solvent.

Although it does not restrict | limit especially as a water-soluble organic solvent, Generally, what has volatility at room temperature from a viewpoint that it can remove easily by drying is suitable. 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.
Specific examples of such volatile water-soluble organic solvents include methanol, ethanol, propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of harmfulness to living organisms, ethanol, propanol or acetone is preferable.

  Further, instead of the water-soluble organic solvent described above or together with the water-soluble organic solvent (that is, as a mixed solvent), water can be used as a solvent. The use of water is particularly suitable for ensuring the amount of tetravalent titanium ions (b) and for uniformly dispersing the ions in the adhesive composition.

  In the present invention, an appropriate amount of the solvent is used for the water-soluble organic solvent and water. For example, the amount of the water-soluble organic solvent is generally the polymerizable monomer component (a) 100. An amount of 10 to 500 parts by weight, in particular 20 to 350 parts by weight, is preferred per part by weight. Further, the amount of water is preferably 5 to 100 parts by weight, particularly 10 to 50 parts by weight per 100 parts by weight of the polymerizable monomer component (a). It is most preferable to use the solvent and water in the above-mentioned range.

[Other ingredients]
The adhesive composition containing the monomer component (a) and containing the tetravalent titanium ion (b) may be blended with various compounding agents known per se, such as a polymerization initiator. (D), fluoride ion (e), etc. can be mix | blended.

Polymerization initiator (d);
The polymerization initiator is not particularly necessary when this adhesive composition is used as a primer for adhesively fixing various materials (for example, adhesives and dental restoration materials), but when used as an adhesive. Is required to cure by itself.
Such a polymerization initiator is preferably a photopolymerization initiator because it can start polymerization in the oral cavity or start polymerization at an arbitrary timing. As the photopolymerization initiator, a compound that itself generates radical species by light irradiation or a mixture obtained by adding a polymerization accelerator to such a compound is used.

Examples of the compound that itself decomposes upon irradiation with light to generate a polymerizable radical species include the following.
α-diketones;
Camphorquinone, benzyl, α-naphthyl, acetonaphthene,
Naphthoquinone, 1,4-phenanthrenequinone,
3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and the like.
Thioxanthones;
2,4-diethylthioxanthone and the like.
α-aminoacetophenones;
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-diethylamino-1- (4-morpholinophenyl)-
Pentanone and the like.
Acylphosphine oxide derivatives;
2,4,6-trimethylbenzoyldiphenylphosphine oxide,
Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide and the like.

In addition, tertiary amines, barbituric acids, mercapto compounds, and the like are used as the above-described polymerization accelerator. Specific examples thereof are as follows.
Tertiary 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-dimethylanthranic 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-dimethylhexylamine,
N, N-dimethyldodecylamine,
N, N-dimethylstearylamine,
N, N-dimethylaminoethyl acrylate,
N, N-dimethylaminoethyl methacrylate,
2,2 ′-(n-butylimino) diethanol and the like.

Barbituric acids;
5-butyl barbituric acid,
1-benzyl-5-phenylbarbituric acid and the like.

Mercapto compounds;
Dodecyl mercaptan,
Pentaerythritol tetrakis (thioglycolate) and the like.

  Further, when the adhesive composition is used as a tooth surface primer for a composite resin containing a peroxide such as hydroperoxide, a vanadium compound may be added as a polymerization initiation aid. The vanadium compound blended in the primer reacts with the peroxide in the composite resin to generate radicals, thereby improving the adhesion between the tooth and the composite resin. The vanadium compound has an oxidation number ranging from -I to + V, but the vanadium compound used in the present invention is particularly preferably a + IV or + V valent vanadium compound because of its high stability and activity. As the + IV value or + V value vanadium compound, known compounds can be used without limitation. Specific examples include divanadium tetroxide (IV), vanadium acetylacetonate (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) Examples of vanadium compounds such as vanadium (IV), oxovanadium (IV) bismaltolate, vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V), vanadium (V) oxytriisopropoxide It is done. Of these, vanadium oxide acetylacetonate (IV), oxovanadium (IV) bismaltolate, and vanadium (V) oxytriisopropoxide are preferable from the viewpoint of solubility in primers, and oxovanadium (IV) bismaltolate is most preferred. preferable.

  The blending amount of such a polymerization initiator (d) is not particularly limited as long as it is an effective amount capable of curing the adhesive composition, and may be set as appropriate. The amount may be in the range of 0.01 to 10 parts by weight, particularly 0.1 to 5 parts by weight per 100 parts by weight of component (a). If the blending amount is too small, polymerization tends to be insufficient, and if it is too large, the strength of the cured product tends to decrease.

Fluoride ion (e);
In the present invention, the fluoride ion (e) is used for ensuring the storage stability of the adhesive composition in the package (B), particularly when the adhesive composition contains water. It is effective to ensure storage stability when water is preferably present therein.

That is, since the tetravalent titanium ion (b) is present in this adhesive composition, the titanium ion may react with moisture during long-term storage to form a solid oxide. is there. The formation of such an oxide is remarkable when water is present, but even when water is not present, by repeatedly opening and closing the lid of the package (B), moisture and oxygen in the air are removed from the package ( B) is taken in and an oxide of titanium ions is formed.
However, the formation of titanium ion oxides leads to a decrease in the titanium ion concentration in the adhesive composition, impairing dentin permeability and ionic crosslinkability, and lowering adhesive strength and durability. Will occur. Further, precipitation of titanium ion oxide may clog the nozzle for taking out the contents provided in the package (B). The fluoride ion (e) effectively prevents the formation of such an oxide.

  In addition, the suppression of the formation of oxides of titanium ions by fluoride ions has been experimentally confirmed (see, for example, WO 2010/010901). Part is fluorinated with fluoride ions, and the fluorinated ion cross-linked product is less susceptible to hydrolysis by water and the like, and is stable, and is considered to suppress the formation of oxides.

  Such fluoride ions (e) may be present in an amount that can prevent the precipitation of titanium oxide, but generally 0.4 to 4 per mole of tetravalent titanium ions (b). It should be present in an amount of 0.0 mol, in particular 0.4 to 1.7 mol.

The supply source of the fluoride ion (e) is not limited as long as it is a fluoride capable of releasing fluoride ions.
For example, hydrofluoric acid, metal fluoride, ammonium fluorides, fluoroaluminosilicate glass, and the like are used, and metal fluoride is particularly preferably used. Examples of such metal fluorides include alkali metal fluorides such as sodium fluoride, potassium fluoride, and lithium fluoride; alkaline earth metal fluorides such as calcium fluoride and magnesium fluoride; aluminum fluoride, fluoride Examples include earth metal fluorides such as yttrium, lanthanum fluoride, and ytterbium fluoride; fluorides of Group 4 elements such as titanium fluoride and zirconium fluoride; zinc fluoride and the like. Among these, alkali metal fluorides and fluorides of Group 4 elements are preferable, and alkali metal fluorides are more preferable. Most preferred is sodium fluoride.
Such a fluoride ion supply source, together with the titanium ion supply source described above, mixes with the acidic monomer (a1) and the solvent (c) to release a predetermined amount of fluoride ion (e), and titanium Ion oxide formation is suppressed.

  As long as the composition is uniform, the fluoride ion (e) in the adhesive composition is almost ionized and exists in the composition, but it elutes from the fluoroaluminosilicate glass. In the case of making it, the content can be determined by measuring by anion chromatography. Specifically, it is pure and diluted to a concentration of 1%, and the resulting diluted solution is filtered through a syringe filter to remove solid components. The fluoride ion concentration contained in the obtained filtrate can be measured by anion chromatography, and the fluoride ion content in the adhesive composition can be calculated.

Other compounding agents;
In addition to the above components (a) to (e), for example, an inorganic filler may be added to the adhesive composition of the package (B) in order to improve the mechanical strength and water resistance of the cured product. it can.
Examples of such inorganic fillers include borosilicate glass, soda glass, glass containing heavy metals (eg, barium, strontium, zirconium), aluminosilicate, glass ceramics, silica, silica / zirconia, silica / titania, silica / alumina, etc. A composite inorganic oxide etc. are mentioned, Among these, silica is the most preferable.

  These inorganic fillers can be improved in mechanical strength and water resistance by being hydrophobized with a surface treatment agent typified by a silane coupling agent to improve the compatibility with the polymerizable monomer. 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 various fillers can be used alone or in admixture of two or more.

  The compounding amount of the inorganic filler described above is generally about 5 to 200 parts by mass, particularly about 10 to 100 parts by mass, per 100 parts by mass of the polymerizable monomer component (a).

  Further, in the present invention, as long as the adhesive composition of the adhesive composition is not impaired, other components known as a compounding component of the dental adhesive composition, for example, an ultraviolet absorber, a polymerization inhibitor, A polymerization inhibitor, a dye, a pigment and the like may be blended.

  The above-mentioned adhesive composition can be produced in the same manner as a known adhesive composition for a tooth. For example, all components to be blended are weighed under an inert light such as red light to obtain a uniform solution. It is manufactured by mixing well until it is, and the manufactured adhesive composition is filled in the package (B).

<Other packages>
In the dental adhesive kit of the present invention, other packages may be used in addition to the packages (A) and (B) depending on the usage form of the adhesive composition in the package (B).

  That is, in the dental adhesive kit of the present invention, the phosphoric acid etching material of the package (A) is applied to the tooth surface to be repaired and etched, and the treated tooth surface is washed with water. Then, the priming process is performed by applying the adhesive composition of the package (B) while the tooth surface is wet (or may be dried by air blow or the like). After this priming treatment, a dental restoration such as a composite resin or a prosthesis, or an orthodontic appliance such as a bracket is bonded and fixed to the tooth appropriately using a dental adhesive.

  However, the above-mentioned adhesive composition, in which the polymerization initiator (d) is blended, can be used as an adhesive for teeth. That is, the adhesive composition that has penetrated into the tooth after the priming treatment is cured by visible light irradiation using a dental irradiator, and then is applied to a dental restoration or orthodontic appliance. Can be adhesively fixed. In this case, this dental adhesive kit may be only two types of packages (A) and (B), and will be used without other packages.

The above composition can also be used as a primer for adhesively fixing the composite resin to the tooth. In this case, after the priming treatment, the paste-like composite resin can be applied immediately without performing a curing treatment such as light irradiation, and can be cured by light irradiation as described above. That is, in the adhesive composition penetrating into the tooth, the polymerization initiator blended in the composite resin penetrates into the adhesive composition and is cured integrally with the composite resin.
Also in this case, this dental adhesive kit may be only two types of packages (A) and (B), and is used without any other package.

  On the other hand, when a vanadium compound is blended in the adhesive composition and a peroxide is blended in the composite resin as a part of the polymerization initiator, the peroxide penetrates into the adhesive composition and generates radicals. Therefore, it adheres firmly to the tooth. In this case, in addition to the packages (A) and (B) described above, a package containing a dedicated composite resin is required.

Furthermore, this adhesive composition can also be used as a primer for an adhesive that adheres and fixes a dental restoration or the like. In this case, the adhesive composition is immediately applied with a dental adhesive without performing a curing treatment such as light irradiation after the priming treatment, and cured by the same light irradiation as described above. Dental restorations and orthodontic appliances are bonded and fixed.
Therefore, in this case, in addition to the packages (A) and (B) described above, a package containing a dental adhesive is required.

  Such a dental adhesive may be a conventionally known one, and for example, those described in JP 2010-201516 A can be used.

  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.

[Phosphoric acid etching material (A)]
Phosphoric acid: 30% phosphoric acid aqueous solution

[Other etching materials]
Citric acid: 30% citric acid aqueous solution

[Acid group-containing polymerizable monomer (a1)]
PM1: 2-methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate phenyl P: 2-methacryloyloxyethyl phenyl hydrogen
Phosphate MDP: 10-methacryloyloxydecyl dihydrogen phosphate 6-MHPA: 6- (meth) acryloxyhexyl phosphonoacetate

[Non-acidic polymerizable monomer (a2)]
BIsGMA: 2,2′-bis (4- (2-hydroxy-3-methacryloxy)
Propoxy) phenyl) propane D-2.6E: 2,2-bis [(4-methacryloyloxypolyethoxy)
Phenyl) propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate MTA: methacrylic acid BAAP: 1,3-bisacrylamidepropane

[Titanium (IV) ion (b)]
TI (O-I-Pr) ₄ : Titanium tetraisopropoxide TI (On-Bu) ₄ : Titanium tetrabutoxide

[Other metal ions]
Zr (O-I-Pr) ₄ : zirconium tetraisopropoxide Hf (OEt) ₄ : hafnium tetraethoxide Al (O-I-Pr) ₃ : aluminum triisopropoxide Ca (OI-Pr) ₂ : Calcium diisopropoxide

[Water-soluble organic solvent (c)]
IPA: Isopropyl alcohol acetone

[Polymerization initiator (d)]
Photopolymerization initiator CQ: camphorquinone

[Fluoride ion (e)]
Sodium fluoride: NaF

Other polymerization initiators Perocta H: 1,1,3,3-tetramethylbutyl hydroperoxide BMOV: Oxovanadium (IV) bis (maltrate)

[Polymerization accelerator]
DMBE: ethyl p-N, N-dimethylaminobenzoate

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

[Ultraviolet absorber]
TNP: 2- (2-hydroxy-5-methylphenyl) benzotriazole

[Inorganic filler]
F1: Fumed silica (average particle size 0.007 μm) surface-treated with dimethyldichlorosilane F2: Spherical silica-zirconia (average particle size 0.4 μm) was hydrophobized with γ-methacryloyloxypropyltrimethoxysilane MF: Fluoroaluminosilicate glass powder in which a mixture of a mixture of a spherical silica-zirconia (average particle size 0.07 μm) and a hydrophobized γ-methacryloyloxypropyltrimethoxysilane at a mass ratio of 70:30 (Tokuso ionomer, manufactured by Tokuyama Corporation) using a wet continuous ball mill (SC mill, manufactured by Mitsui Mining Co., Ltd.)
Those pulverized to an average particle size of 0.4 μm.

In the following examples and comparative examples, various measurements were performed by the following methods.
(1) Test piece preparation method I (when the dental adhesive composition is applied as an adhesive for composite resin)
a) When etching is not performed The front teeth of the cow were removed within 24 hours after slaughter, and the enamel and dentin planes were cut out with water using # 600 emery paper so as to be parallel to the lip surface. 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 composite resin adhesive is applied to the simulated cavity and left for 10 seconds, then compressed air is blown for about 10 seconds to dry, and the dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) is used for 10 seconds. Irradiated with light. Furthermore, a dental composite resin (Esterite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon and irradiated with light with a visible light irradiator for 10 seconds to produce an adhesion test piece Ia.
b) When air blow is performed after phosphoric acid etching In the same manner, bovine enamel and dentin planes are cut out, and compressed air is blown onto these faces for about 10 seconds to dry, and then either enamel or dentin is used. Fix a double-sided tape with a 3mm diameter hole on the flat surface, apply phosphoric acid to the hole, leave it for 15 seconds, wash the phosphoric acid with water for 10 seconds or more, spray again with compressed air for about 10 seconds, and dry After that, paraffin wax was fixed in the same manner to form a simulated cavity.
A composite resin adhesive was applied into the simulated cavity and immediately dried by blowing compressed air for about 10 seconds, and similarly irradiated with light for 10 seconds. Furthermore, a dental composite resin was similarly filled thereon and irradiated with light to prepare an adhesion test piece Ib.
c) When air blow is not performed after phosphoric acid etching Similarly, the bovine enamel and dentin planes are cut out, compressed air is blown onto these faces for about 10 seconds and dried, and then either enamel or dentin Fix a double-sided tape with a 3mm diameter hole on the flat surface, apply phosphoric acid to the hole, leave it for 15 seconds, wash the phosphoric acid with water for 10 seconds or more, and absorb moisture with a cotton ball. Similarly, paraffin wax was fixed to form a simulated cavity.
The composite resin adhesive was quickly applied into the simulated cavity and immediately dried by blowing compressed air for about 20 seconds, and similarly irradiated with light for 10 seconds. Furthermore, a dental composite resin was similarly filled thereon and irradiated with light to prepare an adhesion test piece Ic.
d) When air blow is performed after citric acid etching A simulated cavity was formed in the same manner as the test piece Ib except that citric acid was used as an etching material.
A dental adhesive was applied into the simulated cavity and immediately dried by blowing compressed air for about 20 seconds and similarly irradiated with light for 10 seconds. Furthermore, a dental composite resin was similarly filled thereon and irradiated with light to prepare an adhesion test piece Id.

(2) Test piece preparation method II (when the dental adhesive composition is applied as a pretreatment material for composite resin adhesive)
a) When etching is not performed In the simulated cavity formed in the same manner as the specimen Ia, a pretreatment material for a composite resin tooth adhesive is applied, left for 10 seconds, and then dried by blowing compressed air for about 10 seconds. Further, an adhesive for composite resin (Toxomac Bond II) was applied, and similarly irradiated with light for 10 seconds. Furthermore, a dental composite resin was similarly filled thereon and irradiated with light to prepare an adhesion test piece IIa.
b) When air blow is performed after phosphoric acid etching In the simulated cavity formed in the same manner as the test piece Ib, the pretreatment material for the adhesive for composite resin is applied and immediately compressed air is blown for about 10 seconds and dried. Further, an adhesive for composite resin was applied and similarly irradiated with light for 10 seconds. Further, a dental composite resin was similarly filled thereon and irradiated with light to prepare an adhesion test piece IIb.
c) When air blow is not performed after phosphoric acid etching In the simulated cavity formed in the same manner as the test piece Ic, the pretreatment material for the adhesive for composite resin is quickly applied and immediately compressed air is blown for about 20 seconds. After drying, an adhesive for composite resin was further applied and similarly irradiated with light for 10 seconds. Furthermore, a dental composite resin was similarly filled thereon and irradiated with light to produce an adhesion test piece IIc.
d) When air blow is performed after citric acid etching The pretreatment material for the adhesive for composite resin is quickly applied to the simulated cavity formed in the same manner as the test piece Id, and immediately dried by blowing compressed air for about 20 seconds. Further, an adhesive for composite resin was applied and similarly irradiated with light for 10 seconds. Further, a dental composite resin was similarly filled thereon and irradiated with light to prepare an adhesion test piece IId.

(3) Test piece preparation method III (when the dental adhesive composition is applied as a pretreatment material for composite resin)
a) When etching is not performed In the simulated cavity formed in the same manner as the specimen Ia, the pretreatment material for composite resin is applied, left for 10 seconds, dried by blowing compressed air for about 10 seconds, The dental composite resin was filled and irradiated with light for 20 seconds to prepare an adhesion test piece IIIa.
b) When air blow is performed after phosphoric acid etching The pretreatment material for composite resin is applied to the simulated cavity formed in the same manner as the specimen Ib, and immediately dried by blowing compressed air for about 10 seconds. A dental composite resin was filled and irradiated with light in the same manner to prepare an adhesion test piece IIIb.
c) When air blow is not performed after phosphoric acid etching In the simulated cavity formed in the same manner as the test piece Ic, the composite resin pretreatment material was immediately applied, and immediately compressed air was sprayed for about 20 seconds to dry. Further, a dedicated dental composite resin was filled and irradiated in the same manner to produce an adhesion test piece IIIc.
d) When air blow is performed after citric acid etching The pretreatment material for composite resin is applied to the simulated cavity formed in the same manner as the test piece Id, and immediately dried by blowing compressed air for about 10 seconds. A dental composite resin was filled and irradiated with light in the same manner to produce an adhesion test piece IIId.

(4) Method for measuring adhesion strength after endurance test Adhesive test pieces Ia, Ib, Ic, Id, IIa, IIb, IIc, IId, IIIa, IIIb, IIIc, and IIId are placed in a thermal shock tester. After being immersed in a 4 ° C. water bath for 1 minute, the operation of transferring to a 60 ° C. water bath, soaking for 1 minute, and returning to the 4 ° C. water bath again was repeated 3000 times.
After that, using a tensile tester (Autograph, manufactured by Shimadzu Corp.), the tensile strength was measured at a crosshead speed of 2 mm / mIn, and the tensile bond strength between the enamel or dentin and the composite resin was measured. Four tensile bond strengths per test were measured by the above method, and the average value was measured as the bond strength after the endurance test to evaluate the bond durability.

<Example 1>
As a polymerizable monomer, an equimolar mixture of 12 g PM1, 18 g PM2, 24 g BIsGMA, 16 g 3G and 30 g HEMA; as a titanium ion source, 5.9 g titanium isopropoxide; as a polymerization initiator, 1.25 g of camphorquinone, 1.25 g of DMBE; 85 g of IPA as the water-soluble organic solvent; and 0.03 g of BHT as the other components, and after stirring and mixing until uniform, 20 g of distilled water The mixture was stirred and mixed until uniform again to obtain an adhesive for composite resin comprising the adhesive composition of the present invention.
About this adhesive material, the adhesive strength of each test piece was measured. The composition of the adhesive is shown in Table 1, and the evaluation results are shown in Table 2.

<Examples 2 to 17 and Comparative Examples 1 to 10>
According to the method of Example 1, adhesives having different compositions shown in Table 1 were prepared. About the obtained adhesive material for composite resins, the adhesive strength of each test piece was measured. The composition of the adhesive is shown in Table 1, and the results are shown in Table 2.

<Examples 18 to 23 and Comparative Examples 11 to 14>
The pretreatment materials described in Table 3 were prepared in the same manner as the adhesive material of Example 1, and the obtained pretreatment materials were used as the pretreatment materials for the composite resin adhesive material. The results of measuring the adhesive strength of each test piece are shown in Table 4.

<Example 24>
0.06 g CQ, 0.1 g DMBE, 0.1 g for 2.4 g BIsGMA, 5.6 g D-2.6E and 4.0 g 3G used as non-acidic polymerizable monomers Perocta H, 0.11 g of TNP, 0.002 g of HQME and 0.015 g of BHT were added, and the mixture was stirred until it became uniform in the dark to form a matrix. By mixing 3.3 g of the obtained matrix with 6.23 g of F1 and 0.47 g of MF in an agate mortar and degassing under vacuum, a photocurable composite with a filler filling rate of 67.0% is obtained. Resin CR1 was obtained.
In accordance with the method of Example 1, a composite resin pretreatment material having the composition shown in Table 5 was prepared. The adhesive strength of each test piece was measured using the composite resin CR1 and the prepared composite resin pretreatment material. The results are shown in Table 6.

<Examples 25 and 26 and Comparative Examples 15 and 16>
Similarly, a pretreatment material for composite resin having the composition shown in Table 5 was prepared. In addition, when adding NaF, the aqueous solution of a predetermined density | concentration was prepared previously, and it added together with water at the end. The adhesive strength of each test piece was measured using the composite resin CR1 and the prepared composite resin pretreatment material. The results are shown in Table 6.

Claims (6)

In a dental adhesive kit including a package (A) containing a phosphoric acid etching material and a package (B) containing an adhesive composition,
The adhesive composition is
(A) a polymerizable monomer component containing an acidic group-containing polymerizable monomer (a1);
(B) Titanium (IV) ions;
(C) solvent;
A dental adhesive kit characterized by comprising.   The titanium (IV) ion (b) is present in the adhesive composition in an amount of 0.2 to 1.5 mmol per gram of the acidic group-containing polymerizable monomer (a1). The dental adhesive kit according to 1.   The dental adhesive kit according to claim 1 or 2, wherein the polymerizable monomer component (a) has a hydrogen phosphate diester group.   The dental adhesive kit according to any one of claims 1 to 3, wherein the solvent (c) is water, a water-soluble organic solvent, or a mixed solvent thereof.   The dental adhesive kit according to any one of claims 1 to 4, wherein the adhesive composition contains a polymerization initiator (d).   The said adhesive composition contains 0.4-2.0 mol fluoride ion (e) per mol of titanium (IV) ion (b). Dental adhesive kit.