JPWO2019172132A1 - Dental composition package, its manufacturing method and dental composition - Google Patents

Abstract

In a dental composition package containing a one-component acid / water / coupling agent coexisting composition, deterioration of adhesive performance can be further suppressed even after long-term storage. A dental composition containing a homogeneous composition and a container containing the dental composition are included, and the homogeneous composition comprises (A) a silane coupling agent, (B) a water-soluble fluoride salt, (C) an acidic compound, It consists of a composition in which all the components including (D) an organic solvent and (E) water are uniformly mixed, and (B) observed at 250 ppm to -250 ppm in 19F-NMR when the water-soluble fluoride salt is dissolved in water. The ratio of the total integrated value of the spectrum observed in -110 ppm to -140 ppm to the total integrated value of the entire spectrum to be obtained is 70% or more, the dental composition package, the method for producing the same, and the dental product used therein. Composition.

Description

The present invention relates to a dental composition package, a method for producing the same, and a dental composition.

In dental treatment, dental restorations such as curable restoration materials composed of polymerizable monomers containing polymerizable monomers such as dental cements and composite resins and inorganic fillers, and prostheses using dental ceramic materials. Materials may adhere to each other or such dental restoration materials to the dentin. Then, a primer or a bonding material is generally used for the purpose of improving the adhesiveness at this time. The primer or bonding material used for such a purpose is also referred to as a composition containing an acidic compound, a silane coupling agent and water as active ingredients (hereinafter, also referred to as "acid / water / coupling agent coexisting composition". ) Is often used.

For example, Patent Document 1 states that "a) a pretreatment material containing 80.0 to 99.5% by weight of an organic solvent and 0.5 to 20.0% by weight of a silane coupling agent, and b) 40.0. ~ 94.4% by weight organic solvent, a polymerizable monomer having 0.1 to 20.0% by weight of an acid group, 5.0 to 40.0% by weight of a polymerizable monomer and 0.01 to 0.01 A two-component dental adhesive composition of a post-treatment material containing 5.00% by weight of a polymerization initiator; is disclosed. According to the technique described in Patent Document 1, a dental adhesive composition for adhering dental ceramics / resins is provided, which has excellent adhesive strength and adhesive durability without conspicuous boundaries due to repair by a simple operation. To.

Further, Patent Document 2 states, "A hydrophobic acidic group-containing polymerizable monomer (a), a water-soluble polymerizable monomer (b), water (c), and a photopolymerization initiator (d). , An aromatic tertiary amine (e) having an electron-withdrawing group, a crosslinkable polymerizable monomer (f), and a part of the hydrophobic acidic group-containing polymerizable monomer (a). An adhesive composition for partial re-restoration dental treatment, which comprises a basic compound (g) to be reacted to produce a water-soluble salt and a silane coupling agent (h) as an essential compounding agent. It is disclosed. Then, according to the technique described in Patent Document 2, an adhesive composition and a two-agent type for partial re-restoration dental treatment that exhibit excellent adhesive force to dentin and dental restoration materials not only in the initial stage after adhesion but also for a long period of time. Adhesive is provided.

Further, Patent Document 3 describes (1) a specific alkoxysilane monomer containing at least one ethylenically unsaturated polymerizable group, and (2) a polyhydrogen fluoride salt composed of a specific cation and a specific polyhydrogenfluorine anion. , (3) Organic solvents; and (4) Water-containing primer formulations are disclosed. Further, Patent Document 3 further discloses that the adhesive composition for dental restoration made of ceramics does not contain free hydrofluoric acid (HF). Then, according to the technique described in Patent Document 3, the primer can be directly applied to the surface to be treated without prior etching or roughening, and a reliable bond under oral conditions is ensured. Further, a primer formulation having low toxicity and high stability is provided. Further, Patent Document 3 also discloses a one-component acid / water / coupling agent coexisting composition in a state in which all the components constituting the primer formulation are mixed as a specific example of the primer formulation. ..

Further, in a dental composition containing a silane coupling agent, a composition further containing a substance that generates an acid by light irradiation at the time of use is also known. As such a composition, for example, Patent Document 4 states that "(A) radically polymerizable monomer, (B) coupling agent, (C) sensitizing dye, (D) photoacid generator and / or Storage in which each component of an arylborate compound or a sulfinate is mixed into one agent when a photobase generator, (E) a photoradical generator, or a photoacid generator is used as the component (D). "Adhesive composition for dental restorations made of ceramics having a morphology" is disclosed. According to the technique described in Patent Document 4, the adhesiveness is so high that the prior primer treatment can be omitted, and the components constituting the adhesive composition are stably mixed for a long period of time. Since it can be stored, it is possible to provide an adhesive composition that can omit the mixing operation of the reagent immediately before use.

Japanese Unexamined Patent Publication No. 2003-230574 Japanese Unexamined Patent Publication No. 2006-225350 Special Table 2016-513627 JP-A-2007-277114

Normally, when an acidic compound, water, and a silane coupling agent are present in the same system, the hydrolysis / condensation reaction of the silane coupling agent having a hydrolyzable group such as an alkoxy group proceeds due to the action of the acidic compound. To do. Therefore, in the general acid / water / coupling agent coexisting composition exemplified in Patent Documents 1 and 2, usually, when the composition is used, (1) after all the components constituting the composition are mixed and dissolved. The composition is composed of the first agent and the second agent so that the composition is used immediately or (2) the acidic compound, water and the silane coupling agent do not coexist in the same system. It is necessary to store the composition separately and use it by mixing the first agent and the second agent when using the composition.

However, the one-component composition shown in (1) above lacks storage stability. Therefore, every time it is necessary to use the acid / water / coupling agent coexisting composition, it is necessary to prepare the acid / water / coupling agent coexisting composition, and the operation at the time of use is complicated. is there. On the other hand, in the form of the two-component composition shown in (2) above, it is easy to secure storage stability. However, when using the acid / water / coupling agent coexisting composition, it is necessary to mix the first agent and the second agent, and the operation at the time of use is complicated.

On the other hand, in the composition containing the silane coupling agent and the photoacid generator exemplified in Patent Document 4, when the composition is irradiated with light as an acid catalyst required for the hydrolysis / condensation reaction of the silane coupling agent. A photoacid generator that generates only acid components is used. Therefore, it is not necessary to use an acidic compound in the composition containing the silane coupling agent and the photoacid generator. In addition to this, stable storage for a long period of time is possible in the state of a one-component composition in which all the components constituting the composition containing the silane coupling agent and the photoacid generator are mixed and dissolved. Is. However, light irradiation is required when using a composition containing a silane coupling agent and a photoacid generator. Therefore, in order to obtain the desired effect, a technique for reliably performing light irradiation is required, and a dedicated light irradiation device is also required in terms of equipment.

On the other hand, Patent Document 3 also discloses that the one-component acid / water / coupling agent coexisting composition disclosed as a specific example of the primer formulation has high stability. The fact that such an acid / water / coupling agent coexisting composition has high stability in the form of a one-component composition requires more operation during use than the techniques described in Patent Documents 1 to 3. It is more advantageous in that it can be simplified or the light irradiation technology / equipment can be eliminated. Therefore, the present inventors have studied a one-component acid / water / coupling agent coexisting composition disclosed in Patent Document 3. However, when the present inventors evaluated the adhesiveness of this one-component acid / water / coupling agent coexisting composition after storing it for a long period of time, the adhesive performance deteriorated and the performance was insufficient. It was confirmed that there was.

The present invention has been made in view of the above circumstances, and in a dental composition package containing a one-component acid / water / coupling agent coexisting composition, the adhesive performance is deteriorated even after long-term storage. It is an object of the present invention to provide a dental composition package capable of further suppressing the above, a method for producing the dental composition package, and a dental composition used for the dental composition package.

The above object is achieved by the following invention. That is, the dental composition package of the present invention is
A dental composition containing a uniform composition and a container containing the dental composition.
<I> The uniform composition
(A) Silane coupling agent: 100 parts by mass and
(B) Water-soluble fluoride salt and
(C) Acidic compound: 1 part by mass or more and 10000 parts by mass or less
(D) Organic solvent: 10 parts by mass or more and 90000 parts by mass or less,
(E) Water: 10 parts by mass or more and 2000 parts by mass or less,
Consists of a composition in which all components including
<Ii> The (A) silane coupling agent is
(A) A silicon atom in which a polymerizable group and one to three hydrolyzable groups are bonded in the molecule (excluding the silicon atom represented as "Si" in the following structural formula (1s)). Including and
(B) The hydrolyzable group is selected from the group consisting of (b1) an alkoxy group having 1 to 30 carbon atoms, (b2) a substituted siloxy group represented by the following structural formula (1s), and (b3) a hydrogen atom. Is the basis for being
(C) When three (b1) alkoxy groups as the hydrolyzable groups are bonded to the silicon atom, the carbon number of these three (b1) alkoxy groups is 2 or more and 30 or less.
It is a silicon compound

[In the structural formula (1s), R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively. ]
<Iii> In ¹⁹ F-NMR when the water-soluble fluoride salt (B) was dissolved in water, it was observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm. The total ratio of the integrated values of the spectra is 70% or more, and
<Iv> The content of the water-soluble fluoride salt (B) contained in the uniform composition is within the range satisfying the following formula (1).
It is characterized by that.
-Equation (1) 0.001 ≤ Bm / Am ≤ 6
[In the formula (1), Am means the total number of moles (mol) of the hydrolyzable group contained in 100 parts by mass of the silane coupling agent of the (A), and Bm is the (B). It means the total number of moles (mol) of fluorine atoms derived from a water-soluble fluoride salt. ]

In one embodiment of the dental composition package of the present invention, the (A) silane coupling agent is the following first silane coupling agent, the following second silane coupling agent, and the following third silane coupling agent. It is preferable to contain at least one silane coupling agent selected from the group consisting of.
[First silane coupling agent]: A silane coupling agent composed of a silicon compound represented by the following structural formula (1).

(In the structural formula (1),
V ¹¹ is a methyl group, or a hydrogen atom,
W ¹¹ is an oxygen atom or an imino group,
R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
Each of X ¹¹ , Y ¹¹ , and Z ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms in (b1), or the substituted siloxy represented by the structural formula (1s) in (b2). Is the basis
At least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a substituted siloxy group represented by the structural formula (1s) (b2). )
[Second silane coupling agent]: A silane coupling agent composed of a silicon compound represented by the following structural formula (2).

(In the structural formula (2),
V ²¹ is a methyl group or a hydrogen atom.
W ²¹ is an oxygen atom or an imino group,
R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
Each of X ²¹ and Z ²¹ is a hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms (b1), or the substituted siloxy group represented by the structural formula (1s) (b2). .. )
[Third Silane Coupling Agent]: A silane coupling agent composed of a silicon compound represented by the following structural formula (3).

(In the structural formula (3),
V ³¹ is a methyl group or a hydrogen atom.
W ³¹ is an oxygen atom or an imino group,
R ³¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
Each of X ³¹ , Y ³¹ , and Z ³¹ is independently a hydrocarbon group having 1 to 30 carbon atoms or the (b1) alkoxy group having 1 to 30 carbon atoms. However, at least one group selected from X ³¹ , Y ³¹ , and Z ³¹ is an alkoxy group having 2 to 5 carbon atoms. )

In another embodiment of the dental composition package of the present invention, it is preferable that the (C) acidic compound contains (C1) an acidic group-containing polymerizable monomer.

In another embodiment of the dental composition package of the present invention, the dental composition is selected from the group consisting of a one-component dental adhesive composition and a one-component dental primer composition. The composition is preferably.

In another embodiment of the dental composition package of the present invention, it is preferable that the dental composition comprises only the uniform composition.

The method for producing the dental composition package of the present invention is:
(A) Silane coupling agent: 100 parts by mass and
(B) Water-soluble fluoride salt: A blending amount in terms of parts by mass when the above formula (1) is satisfied, and
(C) Acidic compound: 1 part by mass or more and 10000 parts by mass or less
(D) Organic solvent: 10 parts by mass or more and 90000 parts by mass or less,
(E) Water: 10 parts by mass or more and 2000 parts by mass or less,
A dental composition preparation step of preparing the dental composition containing the uniform composition by mixing all the raw material components including
A filling step of filling the container with the dental composition and
It is characterized by including.

The dental composition of the present invention
Contains a homogeneous composition,
<I> The uniform composition
(A) Silane coupling agent: 100 parts by mass and
(B) Water-soluble fluoride salt and
(C) Acidic compound: 1 part by mass or more and 10000 parts by mass or less
(D) Organic solvent: 10 parts by mass or more and 90000 parts by mass or less,
(E) Water: 10 parts by mass or more and 2000 parts by mass or less,
Consists of a composition in which all components including
<Ii> The (A) silane coupling agent is
(A) A silicon atom in which a polymerizable group and one to three hydrolyzable groups are bonded in the molecule (excluding the silicon atom represented as "Si" in the following structural formula (1s)). Including and
(B) The hydrolyzable group is selected from the group consisting of (b1) an alkoxy group having 1 to 30 carbon atoms, (b2) a substituted siloxy group represented by the following structural formula (1s), and (b3) a hydrogen atom. Is the basis for being
(C) When three (b1) alkoxy groups as the hydrolyzable groups are bonded to the silicon atom, the carbon number of these three (b1) alkoxy groups is 2 or more and 30 or less.
It is a silicon compound

[In the structural formula (1s), R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively. ]
<Iii> In ¹⁹ F-NMR when the water-soluble fluoride salt (B) was dissolved in water, it was observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm. The total ratio of the integrated values of the spectra is 70% or more, and
<Iv> The content of the water-soluble fluoride salt (B) contained in the uniform composition is within the range satisfying the following formula (1).
It is characterized by that.
-Equation (1) 0.001 ≤ Bm / Am ≤ 6
[In the formula (1), Am means the total number of moles (mol) of the hydrolyzable group contained in 100 parts by mass of the silane coupling agent of the (A), and Bm is the (B). It means the total number of moles (mol) of fluorine atoms derived from a water-soluble fluoride salt. ]

According to the present invention, in a dental composition package containing a one-component acid / water / coupling agent coexisting composition, a dental composition capable of further suppressing deterioration of adhesive performance even after long-term storage. It is possible to provide a product package, a method for producing the dental composition package, and a dental composition used for the dental composition package.

The dental composition package of the present embodiment includes a dental composition containing a uniform composition and a container for accommodating the dental composition. Here, in the dental composition package of the present embodiment, the dental composition of the present embodiment satisfying the conditions shown in the following <i> to <iv> is used as the dental composition.

<I> The uniform composition contained in the dental composition includes (A) a silane coupling agent: 100 parts by mass, (B) a water-soluble fluoride salt, and (C) an acidic compound: 1 part by mass or more and 10,000 parts by mass. A composition in which components containing (D) organic solvent: 10 parts by mass or more and 90,000 parts by mass or less, and (E) water: 10 parts by mass or more and 2000 parts by mass or less are uniformly mixed.

<Ii> (A) The silane coupling agent is a silicon compound satisfying the conditions shown in the following (a) to (c).
(A) The molecule of the silane coupling agent contains a polymerizable group and a silicon atom to which one to three hydrolyzable groups are bonded (hereinafter, may be referred to as "first silicon atom"). Here, the silicon atom represented as "Si" in the following structural formula (1s) (hereinafter, may be referred to as "second silicon atom") is excluded from the first silicon atom.
The hydrolyzable group is selected from the group consisting of (b1) an alkoxy group having 1 to 30 carbon atoms, (b2) a substituted siloxy group represented by the following structural formula (1s), and (b3) a hydrogen atom. It is a base.
(C) When three (b1) alkoxy groups as hydrolyzable groups are bonded to the first silicon atom, the number of carbon atoms of the (b1) alkoxy group is 2 or more and 30 or less.

In the structural formula (1s), R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively.

<Iii> (B) In ¹⁹ F-NMR when the water-soluble fluoride salt is dissolved in water, it is observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm. The total ratio of the integrated values of the spectra (hereinafter, may be referred to as “NMR spectrum ratio”) is 70% or more.

<Iv> The content of the water-soluble fluoride salt (B) contained in the homogeneous composition is within the range satisfying the following formula (1).
-Equation (1) 0.001 ≤ Bm / Am ≤ 6
[In the formula (1), Am means the total number of moles (mol) of hydrolyzable groups contained in 100 parts by mass of the silane coupling agent (A), and Bm is (B) water-soluble fluoride. It means the total number of moles (mol) of fluorine atoms derived from the salt. ]

In the homogeneous composition contained in the dental composition of the present embodiment, (A) a silane coupling agent, (B) a water-soluble fluoride salt, (C) an acidic compound, (D) an organic solvent and (E) water All the components constituting the uniform composition containing the above are uniformly mixed. Therefore, the total amount of the solute component containing (A) silane coupling agent, (B) water-soluble fluoride salt and (C) acidic compound is contained in the mixed solvent component containing (D) organic solvent and (E) water. It exists in a uniformly dispersed and dissolved state.

Here, (A) a silane coupling agent, (B) a water-soluble fluoride salt, (C) an acidic compound, (D) an organic solvent and (E) water each interact or react with other components. As a result, at least a part of the hydrolyzable groups constituting the silicon compound constituting the <i> (A) silane coupling agent is replaced with a fluorine atom, and <ii> at least a part of the remainder of the hydrolyzable group is replaced with a fluorine atom. Free fluoride ions are present in the <iii> homogeneous composition substituted with a hydroxyl group.

The dental composition of the present embodiment is a one-component acid / water / coupling agent coexisting composition containing (A) a silane coupling agent, (C) an acidic compound and (E) water. The uniform composition contained in the dental composition is a composition that stably exists in the state shown in the above <i> to <iii>. Therefore, the dental composition of the present embodiment has an excellent effect that is not present in the general acid / water / coupling agent coexisting composition exemplified in Patent Documents 1 and 2, that is, the composition. The effect of further suppressing deterioration of adhesive performance even when stored for a long period of time in the state of a one-component composition containing all the components constituting the composition, not in the state of a two-component composition divided into two solutions. Play. This effect is also superior to that of the one-component acid / water / coupling agent coexisting composition described in Patent Document 3.

The specific reason why the dental composition of the present embodiment exerts the above-mentioned excellent effects is unknown. However, the present inventors do not attribute such effects to the mechanism described in the following item (7) obtained based on the confirmation / examination results listed in the following items (1) to (6). I presume that. However, of course, the above effect may be exerted by a mechanism other than the estimation mechanism shown in the following item (7).

(1) Adhesive performance stability of various acid / water / coupling agent coexisting composition Patent Document 3 describes a primer formulation containing a polyhydrogen fluoride salt (acid / water / coupling agent coexisting composition). However, it is disclosed that it has high stability. Here, the high stability of the primer formulation is evaluated by the ¹⁹ F-NMR measurement results of the primer formulation after long-term storage (after storage at 50 ° C. for 8 weeks). From the results of ¹⁹ F-NMR measurement, it was confirmed that free hydrofluoric acid HF was not present in the primer formulation after long-term storage. Therefore, the inventors of Patent Document 3 have found that the NMR spectrum obtained by the above NMR measurement shows the hydrolysis and HF release of the primer formulation containing the polyhydrogen fluoride salt (hereinafter, “to HF release / hydrolysis stability”). It is concluded that it supports the stability against "sex" (Patent Document 3 / paragraph 093).

However, Patent Document 3 does not show any quantitative evaluation results of the adhesive performance (hereinafter, also referred to as "adhesive performance stability") after long-term storage of the primer formulation containing the polyhydrogen fluoride salt. Not. Therefore, the present inventors adhere to an acid / water / coupling agent coexisting composition containing a polyhydrogen fluoride salt described in Patent Document 3, which is similar to the primer formulation described in Patent Document 3. Performance stability was evaluated (see Comparative Examples 12 and 13 described later). As a result, the adhesive performance stability of the acid / water / coupling agent coexisting composition containing the polyhydrogen fluoride salt described in Patent Document 3 is as high as that of the conventional acid / water / water containing the polyhydrogen fluoride salt. Although it is higher than the adhesive performance stability of the coupling agent coexisting composition (see Comparative Example 6 described later), the adhesive performance stability of the dental composition of the present embodiment (see, for example, Example 5 described later). It was confirmed that it was inferior to that.

(2) Chemical shift of fluoride salt The dental composition of the present embodiment and the primer formulation described in Patent Document 3 are common in that they contain a fluoride salt, but as described above, between the two. There is a difference in adhesive performance stability. Therefore, in order to investigate the reason why the difference in adhesive performance stability between the two occurs, the present inventors have (B) a water-soluble fluoride salt used in the dental composition of the present embodiment, and Patent Document 3 ¹⁹ F-NMR measurement was carried out on an aqueous solution in which the polyhydrogen fluoride salt used in the above-mentioned primer formulation was dissolved in water.

As a result, for (B) water-soluble fluoride salt, almost all peaks were observed in the region of -110 ppm to -140 ppm in which the chemical shift (δ) was relatively large. On the other hand, with respect to the polyhydrogen fluoride salt described in Patent Document 3, although peaks are observed in the region of -110 ppm to -140 ppm, the ratio is small, and most of them are in the region where δ is smaller than -140 ppm. A peak was observed. Therefore, based on the result shown in the above item (1), it is estimated that the intensity of the peak observed in the region of -110 ppm to -140 ppm, in other words, the NMR spectrum ratio is closely related to the adhesive performance stability. Will be done.

(3) Molecular Structure of Silane Coupling Agent A silane coupling agent in which all hydrolyzable groups are composed of (highly hydrolyzable) methoxy groups is most widely used because of its high effect. .. However, in a dental composition using such a silane coupling agent, it was confirmed that the adhesive performance stability was insufficient even when (B) a water-soluble fluoride salt was used in combination (comparison described later). See Example 14).

(4) Existence form of the dental composition of the present embodiment after preparation In order to investigate the existence form of the dental composition of the present embodiment, the dentistry of the present embodiment of Examples 1, 5, 9 and 10 described later Various NMR measurements were carried out on the sample after the composition for use was left at 25 ° C. for 1 day. As a result, the dental composition of the present embodiment contains <i> Si-F ( ¹⁹ F-NMR: -157 ppm, ²⁹ Si-NMR: 36 ppm) and <ii> Si-OH ( ²⁹ Si-NMR: 14 ppm). ) And <iii> free fluorine ions (fluorine ions: ¹⁹ F-NMR: -135 ppm) were confirmed to be present.

(5) Molar ratio (Bm / Am) of the hydrolyzable group contained in (A) the silane coupling agent and the fluorine atom derived from (B) the water-soluble fluoride salt.
In a dental composition containing all of the components (A) to (E), when the molar ratio (Bm / Am) is within a predetermined range as shown in the formula (1), the adhesive performance stability is more excellent. (Examples 1-20, Comparative Example 7, and Comparative Example 11 described later).

As is clear from the above description in (4), "(B) a fluorine atom derived from a water-soluble fluoride salt" means (i) a raw material before preparing a dental composition. It corresponds to the fluorine atom contained in (B) the water-soluble fluoride salt in the state, and (ii) means the fluorine atom existing as Si-F and free fluorine ion in the prepared dental composition. ..

(6) Existence State of Polyhydrogen Fluoride Salt Described in Patent Document 3 In Table 3-1 of Patent Document 3, FIG. 1, FIG. 2, and paragraph 0094, ¹⁹ F- of the polyhydrogen fluoride salt described in Patent Document 3 is shown. The results of NMR measurements are disclosed. From this measurement result, the facts shown in the following (a)-(c) can be grasped.
(A) The polyhydrogen fluoride anion constituting the polyhydrogen fluoride salt described in Patent Document 3 has a peak in the range of -146.7 ppm to -155.2 ppm.
(B) In the peak described in (a) above, the chemical shift value tends to decrease as the content of HF contained in the polyhydrogen fluoride salt increases. Here, in (b), an increase in the HF content means that the degree of influence of hydrogen bonds increases.
(C) The peak of HF exists at -165 ppm.

And, as shown in FIG. 2 of Patent Document 3, despite the coexistence of the silane coupling agent, the acidic compound and water, the peak of the polyhydrogen fluorine anion is almost reduced even after a long period of time. Absent.

The specific measurement conditions for ¹⁹ F-NMR disclosed in the present specification and the specific measurement conditions for ¹⁹ F-NMR disclosed in paragraph 0094 of Patent Document 3 are the same as the solvent used. Does not match. Therefore, the chemical shift values for the same substance do not completely match between the two.

(7) Estimating mechanism for exerting the effect When the confirmation / examination results shown in the above items (1) to (6) are combined, it is estimated that the effect of the dental composition of the present embodiment is exhibited by the mechanism described below. Will be done.

First, the silicon compound constituting the (A) silane coupling agent reacts in the coexistence of trace amounts of free fluorine ions, water and acid. Here, the hydrolyzable group is dehydrated and condensed after being hydrolyzed to form a siloxane bond. Then, the formed siloxane bond is cleaved by the fluoride ion to form a Si—OH bond and a Si—F bond. By such a series of processes, the hydrolyzable group is finally stabilized in a changed state with a trace amount of Si—F bond and a large amount of Si—OH bond. It is said that fluoride ions may be hydrated in water and exist as F (OH) ^4- , and it is well known that they have a high affinity for Si. It is considered that such performance contributes to the above stabilization.

Based on these points, when a certain amount of time has passed since the dental composition of the present embodiment was prepared, it is hydrolyzed by the formation of Si—F bonds and the proximity of fluoride ions to Si atoms. The sex group will be protected. As a result, the dental composition of the present embodiment is less likely to undergo dehydration condensation between silane coupling agent molecules during storage, and is maintained in an extremely stable state. On the other hand, when the dental composition of the present embodiment is used, the above-mentioned stabilized state is obtained by a drying operation such as air blowing performed after the dental composition of the present embodiment is applied to the object to be treated. Will be destroyed. At this time, the reactivity of the dental composition of the present embodiment is restored, and high adhesive performance is exhibited.

On the other hand, the polyhydrogen fluorine anion does not have the effect of stabilizing the hydrolyzable group as described above. In addition, the amount of fluoride ions generated from the polyhydrogen fluoride salt described in Patent Document 3 is small. In addition, there is also the effect of interaction with the polyhydrogen fluorine anion (eg equilibrium, etc.). Therefore, it is considered that the adhesive performance stability when the polyhydrogen fluoride salt described in Patent Document 3 is used is inferior to that of the dental composition of the present embodiment.

The details of the dental composition of the present embodiment and each component contained therein will be described below.

<(A) Silane coupling agent; (A) component>
As the silane coupling agent, silicon compounds satisfying the conditions shown in the following (a) to (c) are used.
(A) The molecule of the silane coupling agent contains a polymerizable group and a silicon atom (first silicon atom) to which one to three hydrolyzable groups are bonded.
The hydrolyzable group is selected from the group consisting of (b1) an alkoxy group having 1 to 30 carbon atoms, (b2) a substituted siloxy group represented by the following structural formula (1s), and (b3) a hydrogen atom. It is a base.
(C) When three (b1) alkoxy groups as hydrolyzable groups are bonded to the first silicon atom, the number of carbon atoms of the (b1) alkoxy group is 2 or more and 30 or less.

From the first silicon atom, the silicon atom contained in the substituted siloxy group shown in the following structural formula (1s) (the second silicon atom (the silicon atom represented as "Si" in the structural formula (1s)) is Further, the silicon atom represented as "Si" in the structural formulas (1) to (3) described later corresponds to the first silicon atom.

In the structural formula (1s), R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively.

Among the hydrolyzable groups, the methoxy group has the highest hydrolyzability and lacks stability. Therefore, a silane coupling agent in which three methoxy groups are bonded to the primary silicon atom as hydrolyzable groups (for example, γ-methacryloxypropyltrimethoxysilane and γ-methacry, which are widely used in dental applications). With loxypropylmethyldimethoxysilane, vinyltrimethoxysilane, etc.), sufficient adhesion performance stability cannot be obtained. Therefore, as shown in item (c) above, the silane coupling agent in which three methoxy groups are directly bonded to the first silicon atom is excluded from the silane coupling agent used in the dental composition of the present embodiment. Has been done. From the same viewpoint, when the hydrolyzable group is a (b1) alkoxy group, the number of carbon atoms thereof is preferably 2 to 30.

The silane coupling agent used in the dental composition of the present embodiment is not particularly limited as long as it is a silicon compound satisfying the above conditions (a) to (c), but from the viewpoint of adhesiveness and storage stability, it is not particularly limited. The first silane coupling agent composed of the silicon compound represented by the following structural formula (1), the second silane coupling agent composed of the silicon compound represented by the following structural formula (2), and the following structural formula (3). It is particularly preferable to contain at least one silane coupling agent selected from the group consisting of a third silane coupling agent consisting of a silicon compound. The silane coupling agents will be described in detail below.

(First silane coupling agent)
The first silane coupling agent that can be used in the dental composition of the present embodiment comprises a silicon compound represented by the following structural formula (1).

In structural formula (1),
V ¹¹ is a methyl group, or a hydrogen atom,
W ¹¹ is an oxygen atom or an imino group,
R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
X ¹¹ , Y ¹¹ , and Z ¹¹ are hydrocarbon groups having 1 to 30 carbon atoms, (b1) alkoxy groups having 1 to 30 carbon atoms, or (b2) substituted siloxy groups represented by the structural formula (1s), respectively. Yes,
At least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a substituted siloxy group represented by (b2) structural formula (1s).

In the above formula (1), V ¹¹ is a methyl group or a hydrogen atom. Of these, a methyl group is preferable in consideration of excellent adhesiveness.

In the formula (1), W ¹¹ is an oxygen atom or an imino group (-NH-).

In the formula (1), R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms. Among them, in consideration of excellent storage stability and adhesiveness, R ¹¹ is preferably an alkylene group having 1 to 10 carbon atoms, and more specifically, a methylene group, an ethylene group, a trimethylene group, or a propylene group. An alkylene group having 1 to 3 carbon atoms is preferable.

In the above formula (1), X ¹¹ , Y ¹¹ , and Z ¹¹ are hydrocarbon groups having 1 to 30 carbon atoms, (b1) alkoxy groups having 1 to 30 carbon atoms, or (b2) structural formula (1s), respectively. ) Is a substituted hydrocarbon group. Then, at least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a substituted siloxy group represented by the structural formula (1s) (b2).

In X ¹¹ , Y ¹¹ , and Z ¹¹ , examples of the hydrocarbon group having 1 to 30 carbon atoms include saturated hydrocarbon groups such as an alkyl group having 1 to 30 carbon atoms. Examples of the alkyl group having 1 to 30 carbon atoms include linear and branched alkyl groups having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group and an isopropyl group.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , the hydrocarbon group having 1 to 30 carbon atoms may be an unsaturated hydrocarbon group having 1 to 30 carbon atoms. Among them, an unsaturated hydrocarbon group having 1 to 10 carbon atoms is preferable, and a group having a polymerizable group at the terminal such as a vinyl group and an allyl group is preferable in order to exert an excellent effect on adhesiveness.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , as the (b1) alkoxy group having 1 to 30 carbon atoms, an alkoxy group having 2 to 10 carbon atoms is preferable in order to exert an excellent effect, and specifically, an alkoxy group having 2 to 10 carbon atoms is preferable. , Ethoxy group, propoxy group, isopropoxy group, butoxy group.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , at least one is a substituted siloxy group represented by the structural formula (1s) (b2).

In the formula, R ¹² , R ¹³ and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively.

In R ¹² , R ¹³ , and R ¹⁴ , the hydrocarbon groups having 1 to 30 carbon atoms and the alkoxy groups having 1 to 30 carbon atoms have the carbon atoms 1 to 30 described in X ¹¹ , Y ¹¹ , and Z ¹¹ . Examples thereof include a hydrocarbon group or (b1) an alkoxy group having 1 to 30 carbon atoms, and a hydrocarbon group is preferable from the viewpoint of storage stability.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , at least one of them may be a substituted siloxy group represented by (b2) structural formula (1s), and two or three may be substituted siloxy groups represented by (b2) structural formula (1s). It may be a group. Among them, in consideration of excellent storage stability and adhesiveness, it is preferable that two or three of X ¹¹ , Y ¹¹ , and Z ¹¹ are substituted siloxy groups represented by the structural formula (1s) (b2).

As the first silane coupling agent represented by the structural formula (1), a commercially available product can be used. Among them, if a suitable compound is specifically shown as an example, (methacryloxymethyl) bis (trimethylsiloxy) methylsilane, methacryloxypropyltris (vinyldimethylsiloxy) silane, and metharoxypropyl from the viewpoint of further improving storage stability. Tris (trimethylsiloxy) silane, methacryloxytris (trimethylsiloxy) silane, 3-methacryloxypropylbis (trimethylsiloxy) methylsilane, (3-acryloxypropyl) methylbis (trimethylsiloxy) silane, (3-acryloxypropyl) tris (Trimethylsiloxy) silane can be mentioned.

(Second silane coupling agent)
The second silane coupling agent that can be used in the dental composition of the present embodiment comprises a silicon compound represented by the following structural formula (2).

In structural formula (2),
V ²¹ is a methyl group or a hydrogen atom.
W ²¹ is an oxygen atom or an imino group,
R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
X ²¹ and Z ²¹ are hydrocarbon groups having 1 to 30 carbon atoms, (b1) alkoxy groups having 1 to 30 carbon atoms, or (b2) substituted siloxy groups represented by the structural formula (1s), respectively.

In structural formula (2), V ²¹ is a methyl group or a hydrogen atom. Of these, a methyl group is preferable in consideration of excellent adhesiveness.

In the structural formula (2), W ²¹ is an oxygen atom or an imino group (-NH-).

In the structural formula (2), R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, which is the same group as the group described in R ¹¹ shown in the structural formula (1), and is also a suitable group. It is the same as R ¹¹ .

In the structural formula (2), X ²¹ and Z ²¹ are represented by a hydrocarbon group having 1 to 30 carbon atoms, (b1) an alkoxy group having 1 to 30 carbon atoms, or (b2) structural formula (1s), respectively. It is a substituted hydrocarbon group.

In X ²¹ and Z ²¹ , examples of the hydrocarbon group having 1 to 30 carbon atoms include the same groups as those described in X ¹¹ , Y ¹¹ , and Z ¹¹ shown in the structural formula (1), which are preferable groups. Is the same.

Similarly, in X ²¹ and Z ²¹ , examples of the alkoxy group having 1 to 30 carbon atoms include the same groups as those described in X ¹¹ , Y ¹¹ , and Z ¹¹ represented by the structural formula (1). The same applies to the preferred groups.

Further, in the substituted siloxy group represented by the structural formula (1s) (b2), R ¹² , R ¹³ and R ¹⁴ are each a hydrocarbon group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, respectively. is there. These hydrocarbon groups having 1 to 30 carbon atoms and alkoxy groups having 1 to 30 carbon atoms are substituted as shown in structural formula (1) as X ¹¹ , Y ¹¹ or Z ^{11 shown} in (b2) structural formula (1s). Examples thereof include the same groups as when a syroxy group is used, and a hydrocarbon group is preferable from the viewpoint of storage stability.

In X ²¹ and Z ²¹ , both are preferably substituted siloxy groups represented by the structural formula (1s) in (b2) in order to particularly improve storage stability and adhesiveness.

As the second silane coupling agent represented by the structural formula (2), a commercially available product can be used. Among them, 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane can be mentioned from the viewpoint of further improving storage stability, to give a specific example of a suitable compound.

(Third silane coupling agent)
The third silane coupling agent that can be used in the dental composition of the present embodiment comprises a silicon compound represented by the following structural formula (3).

In structural formula (3),
V ³¹ is a methyl group or a hydrogen atom.
W ³¹ is an oxygen atom or an imino group,
R ³¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
X ³¹ , Y ³¹ , and Z ³¹ are independently hydrocarbon groups having 1 to 30 carbon atoms or (b1) alkoxy groups having 1 to 30 carbon atoms. However, at least one group selected from X ³¹ , Y ³¹ , and Z ³¹ is an alkoxy group having 2 to 5 carbon atoms.

In structural formula (3), V ³¹ is a methyl group or a hydrogen atom. Of these, a methyl group is preferable in consideration of excellent adhesiveness.

In the structural formula (3), W ³¹ is an oxygen atom or an imino group (-NH-).

In the structural formula (3), R ³¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms, which is the same group as the group described for R ¹¹ shown in the structural formula (1), and is also a suitable group. It is the same as R ¹¹ .

X ³¹ , Y ³¹ , and Z ³¹ are independently hydrocarbon groups having 1 to 30 carbon atoms or (b1) alkoxy groups having 1 to 30 carbon atoms. However, at least one group selected from X ³¹ , Y ³¹ , and Z ³¹ is an alkoxy group having 2 to 5 carbon atoms.

In X ¹¹ , Y ¹¹ , and Z ¹¹ , at least one of them may be an alkoxy group having 2 to 5 carbon atoms, and 2 or 3 may be an alkoxy group having 2 to 5 carbon atoms. Among them, in consideration of excellent storage stability and adhesiveness, it is preferable that two or three of X ¹¹ , Y ¹¹ , and Z ¹¹ are alkoxy groups having 2 to 5 carbon atoms, and X ¹¹ , Y ^11, and it is preferable that all of ^{Z 11} is an alkoxy group having 2-5 carbon atoms. Further, in order to improve storage stability and adhesiveness, the alkoxy group preferably has 3 to 4 carbon atoms.

As the third silane coupling agent represented by the structural formula (3), a commercially available product can be used. Among them, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, and γ-methacryloxypropyltriiso can be further improved in storage stability by giving a specific example of a suitable compound. Examples thereof include propoxysilane, and γ-methacryloxypropyltriisopropoxysilane is particularly preferable.

((A) Blending amount of silane coupling agent)
As the (A) silane coupling agent, only one type may be used, or two or more types may be used in combination. When two or more types are used in combination, the reference mass is the total amount thereof.

In the dental composition of the present embodiment, the blending ratio of the (A) silane coupling agent in the uniform composition is not particularly limited, but is preferably in the range of 0.1% by mass to 70% by mass, and 1% by mass to 1% by mass. The range of 50% by mass is more preferable. If the blending ratio is less than 0.1% by mass, sufficient adhesive strength and storage stability may not be obtained, and if it exceeds 70% by mass, the curability may decrease and the adhesive strength may decrease.

<(B) Water-soluble fluoride salt>
The (B) water-soluble fluoride salt used in the dental composition of the present embodiment is a water-soluble substance. Here, the "water-soluble substance" means a substance having a solubility of 100 mg or more, which is defined by an amount (g or mg) at which a solute can be dissolved in 100 g of water at 25 ° C. In addition, (B) the water-soluble fluoride salt is the integrated value of the spectrum observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm in the ¹⁹ F-NMR measurement. The total ratio is 70% or more. The NMR spectrum ratio is preferably 90% or more, more preferably 100%. If the NMR spectrum ratio is less than 70%, sufficient adhesive performance stability cannot be obtained. ¹⁹ F-NMR measurement is carried out using an aqueous solution obtained by dissolving 0.001 to 0.01 g of (B) water-soluble fluoride salt in 1 g of heavy water.

Therefore, for example, even a substance containing fluorine, which elutes fluoride ions when the substance is mixed with water, is mostly present in water as an insoluble substance (for example, fluoroaluminosilicate glass, etc.). ) Does not correspond to (B) water-soluble fluoride salt. Further, even if it is a water-soluble fluoride salt, a substance having an NMR spectrum ratio of less than 70%, such as the polyhydrogen fluoride salt described in Patent Document 3, does not fall under (B) a water-soluble fluoride salt. ..

(B) Specific examples of the water-soluble fluoride salt are sodium fluoride (-122ppm 100%), potassium fluoride (-122ppm 100%), lithium fluoride (-122ppm 100%), and cesium fluoride (-122ppm 100%). -122ppm 100%), barium fluoride (-122ppm 100%), copper fluoride (-122ppm 100%), zirconium fluoride (-122ppm 100%), aluminum fluoride (-122ppm 100%), titanium fluoride (-122ppm 100%) Metal fluoride salts such as -122ppm 100%), and tetramethylammonium fluoride (-122ppm 100%), tetraethylammonium fluoride (-122ppm 100%), tetra-n-butylammonium fluoride (-129ppm 100%). ) And the like. Of the two numerical values shown in parentheses for each substance listed above, the numerical value (ppm) on the left side indicates the peak position in ¹⁹ F-NMR measurement, and the numerical value (%) on the right side indicates the NMR spectrum ratio. Shown.

In the dental composition of the present embodiment, the content of the water-soluble fluoride salt (B) contained in the uniform composition needs to be within the range satisfying the following formula (1).
-Equation (1) 0.001 ≤ Bm / Am ≤ 6
In the formula (1), Am means the total number of moles (mol) of hydrolyzable groups contained in 100 parts by mass of the silane coupling agent (A), and Bm is the water-soluble fluoride salt (B). It means the total number of moles (mol) of fluorine atoms derived from.

If Bm / Am exceeds 6, sufficient adhesive performance cannot be obtained. It is presumed that this is because most of the hydrolyzable groups constituting the (A) silane coupling agent are replaced with fluorine atoms and cannot participate in adhesion. Further, when Bm / Am is less than 0.001, the storage stability of the dental composition is lowered. It is presumed that this is because it becomes difficult to maintain the (A) silane coupling agent in a stable state during storage. Considering storage stability and adhesiveness, the lower limit of Bm / Am is preferably 0.003 or more, more preferably 0.01 or more, and the upper limit of Bm / Am is preferably 3 or less, and 1.5 or less. More preferably, 0.22 or less is further preferable.

Since Am is the total number of moles (mol) of hydrolyzable groups contained in the (A) silane coupling agent, the (A) silane cup is added to the number of moles of the (A) silane coupling agent blended. It can be determined by multiplying the number of hydrolyzable groups that the ring agent has in the molecule. When a plurality of types of (A) silane coupling agents are used, the amount of hydrolyzable groups is determined for each (A) silane coupling agent, and the total amount is defined as Am. For example, in the case of (methacryloxymethyl) bis (trimethylsiloxy) methylsilane, which is the first silane coupling agent, 1 mol of (methacryloxymethyl) bis (trimethylsiloxy) methylsilane has 2 mol of hydrolyzable groups. It will exist. In the case of 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane, which is the second silane coupling agent, 1 mol of 1,3-bis (3-methacryloxypropyl) tetrakis (trimethyl). In the case of syroxy) disiloxane, 5 mol of hydrolyzable groups will be present. In the case of γ-methacryloxypropyltriisopropoxysilane, which is a third silane coupling agent, 1 mol of γ-methacryloxypropyltriisopropoxysilane means that 3 mol of hydrolyzable groups are present.

<(C) Acid compound>
The (C) acidic compound used in the dental composition of the present embodiment promotes (A) hydrolysis of the silane coupling agent and (C) dehydration condensation of the acidic compound and the silanol group on the surface of the adherend. Functions as an acid catalyst.

(C) The acidic compound means a substance having a pH of 5 or less in an aqueous solution or an aqueous dispersion dissolved and / or dispersed in water at a concentration of 1 mol / L. Examples of the acidic compound (C) include known compounds such as inorganic acids such as hydrochloric acid, nitric acid and phosphoric acid, and organic acids such as acetic acid and citric acid. As the (C) acidic compound, one kind or a combination of two or more kinds can be used. When two or more kinds of (C) acidic compounds are used in combination, the reference mass is the total amount thereof.

(C) Acidic compounds include dentin (dental dentin, enamel), base metals (iron, nickel, chromium, cobalt, tin, aluminum, copper, titanium, etc. or alloys containing these as main components), zirconium, and the like. It is preferable to use (C1) an acidic group-containing polymerizable monomer from the viewpoint of improving the adhesiveness to a metal oxide (zirconia ceramics or the like) containing the metal and oxygen as main components. Therefore, in the case of repairing by adhering a prosthesis made of a base metal or a metal oxide and a dentin, the present implementation using (C1) an acidic group-containing polymerizable monomer as (C) an acidic compound. It is preferable to use the form of the dental composition.

((C1) Acidic group-containing polymerizable monomer)
The (C1) acidic group-containing polymerizable monomer 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 may be used. it can.

Here, the "(C1) acidic group contained in the acidic group-containing polymerizable monomer" is a group in which the aqueous dispersion medium or the aqueous suspension of the polymerizable monomer having an acidic group exhibits acidity. Not only a simple acidic group, but also an acid anhydride structure in which two of the acidic groups are dehydrated and condensed, or an acid halide group in which the acidic group is halogenated may be used. Specifically, the phosphinic group {= P (= O) OH}, the phosphono group {-P (= O) (OH) ₂ }, the carboxyl group {-C (= O) OH}, the dihydrogen phosphate monoester group {-O-P (= O) (OH) 2}, hydrogen phosphate diester group _{{(-O-) 2 P (=} O) OH}, sulfo group _(-SO 3 H), and acid anhydride skeleton {-C (= O) -OC (= O)-} and the like can be mentioned.

Among the acidic groups for which specific examples are listed above, a carboxyl group, a dihydrogen phosphate monoester group, and a hydrogen phosphate diester group are more preferable. These acidic groups are highly stable in water and can slowly dissolve the smear layer on the tooth surface and decalcify the teeth. Further, from the viewpoint of having the highest effect, the dihydrogen phosphate monoester group and the hydrogen phosphate diester group are most preferable.

Specific examples of the polymerizable monomer having a dihydrogen phosphate monoester group or a hydrogen phosphate diester group include 2- (meth) acryloyloxyethyl dihydrogen phosphate and bis [2- (meth) acryloyloxy. Ethyl] Hydrogen phosphate, 2- (meth) acryloyloxyethylphenylhydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 6- (meth) acryloyloxyhexylphenyl hydrogen phosphate, 10- (meth) Acryloyloxydecyldihydrogen phosphate, 1,3-di (meth) acryloylpropan-2-dihydrogenphosphate, 1,3-di (meth) acryloylpropan-2-phenylhydrogenphosphate, bis [5- {2 -(Meta) acryloyloxyethoxycarbonyl} heptyl] hydrogen phosphate and the like.

Specific examples of the polymerizable monomer having a carboxyl group include acrylic acid, methacrylic acid, 4- (meth) acryloxyethyltrimellitic acid, and 11- (meth) acryloyloxy-1,1-undecandycarboxylic acid. , 1,4-Di (meth) acryloyloxypyromellitic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, etc. Can be mentioned.

Specific examples of the polymerizable monomer having a sulfo group include 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid, and vinylsulfonic acid. And so on.

Among the (C1) acidic group-containing polymerizable monomers described above, the polymerizable monomers having the structural formulas listed below are particularly preferable.

In the (C1) acidic group-containing polymerizable monomer shown as the structural formula listed above, R is a hydrogen atom or a methyl group.

Further, these (C1) acidic group-containing polymerizable monomers may be used in combination of two or more, if necessary. When two or more types of (C1) acidic group-containing polymerizable monomers are used in combination, the reference mass is the total amount thereof. As a matter of course, when the (C1) acidic group-containing polymerizable monomer and other (C) acidic compound are used in combination, the mass of the reference (C) acidic compound is the total of them. The quantity.

As the (C) acidic compound, a polymer obtained by polymerizing the (C1) acidic group-containing polymerizable monomer can also be used.

((C) Blending amount of acidic compound)
The blending amount of the (C) acidic compound in the uniform composition is in the range of 1 part by mass to 10000 parts by mass and the range of 10 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the (A) silane coupling agent. Is preferable, and the range of 80 parts by mass to 750 parts by mass is more preferable. (C) If the blending amount of the acidic compound is less than 1 part by mass, the adhesiveness is lowered, and if the blending amount is more than 10,000 parts by mass, the adhesiveness after storage is lowered (storage stability is lowered). ..

<(D) Organic solvent>
As the (D) organic solvent used in the dental composition of the present embodiment, known ones can be used without limitation, and can be appropriately selected depending on the purpose of the dental composition. Specific examples of the organic solvent (D) include alcohols such as methanol, ethanol, isopropyl alcohol, butanol and isobutyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, 1,4-dioxane and tetrahydrofuran; Esters such as ethyl acetate and ethyl formate; aromatic solvents such as toluene, xylene and benzene; hydrocarbon solvents such as pentane, hexane, heptane and octane; chlorine solvents such as methylene chloride, chloroform and 1,2-dichloroethane Solvent; Examples thereof include a fluorine-based solvent such as trifluoroethanol.

Among these, acetone, ethanol, isopropyl alcohol and the like are particularly preferable from the viewpoint of solubility, storage stability and the like. (D) The organic solvent may be used alone or in combination of two or more. When two or more kinds of (D) organic solvents are used in combination, the reference amount is the total amount thereof.

The amount of the (D) organic solvent blended in the dental composition is in the range of 10 parts by mass to 90,000 parts by mass and in the range of 100 parts by mass to 50,000 parts by mass with respect to 100 parts by mass of the (A) silane coupling agent. Is preferable, and the range of 700 parts by mass to 5000 parts by mass is more preferable. If the amount of (D) organic solvent is less than 10 parts by mass with respect to 100 parts by mass of (A) silane coupling agent, the concentrations of (A) silane coupling agent, (C) acidic compound, and (E) water become high. Therefore, the storage stability tends to decrease. Further, if the amount of the (D) organic solvent exceeds 90,000 parts by mass, the concentration of the (A) silane coupling agent becomes diluted and the adhesive strength (adhesiveness) may not be sufficiently obtained.

<(E) Water>
The water (E) preferably contains substantially no harmful impurities from the viewpoint of storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water and distilled water.

The amount of water (E) to be blended is in the range of 10 parts by mass to 2000 parts by mass, preferably in the range of 50 parts by mass to 500 parts by mass with respect to 100 parts by mass of the (A) silane coupling agent. (E) If the amount of water blended is less than 10 parts by mass, the adhesive strength will decrease. Further, when the blending amount of (E) water exceeds 2000 parts by mass, the water remains in the dental composition of the present embodiment applied to the surface of the adherend without being completely removed by air blow, which hinders adhesion. Or, the hydrolysis of the (A) silane coupling agent is promoted too much, and the storage stability is lowered.

<Dental composition and uniform composition>
The dental composition of the present embodiment includes a uniform composition. This homogeneous composition contains components (A) to (E), and if necessary, components other than the components (A) to (E) (hereinafter, may be referred to as "other components") are further contained. You may be. The uniform composition is a liquid, paste-like or sol-like composition in which all the components contained in the composition are uniformly mixed. This homogeneous composition continues to stably maintain the state immediately after preparation over time, and even after being allowed to stand for a long period of time, it can be separated into a solid phase and a liquid phase, or separated into an aqueous phase and an oil phase. Phase separation over time does not occur.

The dental composition of the present embodiment may be composed of only the uniform composition, and is composed of the uniform composition and other compositions that are not mixed with the uniform composition and exist in a separated state. It may have been done. Examples of other compositions include compositions such as inorganic fillers that are insoluble in uniform compositions (hereinafter, may be referred to as "insoluble compositions"). Examples of the components constituting the insoluble composition include other components and (B) water-soluble fluoride salt present in a solid state in the dental composition. When (B) the water-soluble fluoride salt is present in the dental composition in a solid state, (B) has a saturation concentration or higher with respect to the solvent component (particularly (E) water) constituting the uniform composition. A water-soluble fluoride salt will be added to the dental composition. When the dental composition of the present embodiment is composed of a homogeneous composition and an insoluble composition, both can be separated by a separation operation such as decantation or filtration.

When the dental composition of the present embodiment is used as a one-component dental adhesive or a dental primer, it is preferable that the dental composition of the present embodiment is composed of only a uniform composition. .. When the dental composition of the present embodiment containing the uniform composition and the insoluble composition is used, the dental composition of the present embodiment is contained in a container and shaken immediately before use. , It is preferable to uniformly mix the homogeneous composition and the insoluble composition.

<Other ingredients>
As the "other components" that can be blended in the dental composition of the present embodiment, it may be referred to as a polymerizable monomer having no acidic group (hereinafter, "acid group-free polymerizable monomer"". ), Fillers, photopolymerization initiators, polymerization inhibitors, and other substances used in dental compositions can be used as needed. Further, the dental composition of the present embodiment is selected from (C1) an acidic group-containing polymerizable monomer, an acidic group-free polymerizable monomer, and (A) a silane coupling agent containing a radically polymerizable group. A chemical polymerization initiator can be used for the polymerization curing of the dental composition when it contains at least one polymerizable monomer component. In this case, as "other components", at least one component out of a plurality of types of components constituting the chemical polymerization initiator can be blended into the dental composition of the present embodiment. These "other components" will be described below.

<Polymeric monomer containing no acidic group>
Examples of the acidic group-free polymerizable monomer include organic acids such as α-cyanoacrylic acid, (meth) acrylic acid, α-halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid, and itaconic acid. Examples thereof include esters, (meth) acrylamide, and (meth) acrylamide derivatives, vinyl esters, vinyl ethers, mono-N-vinyl derivatives, and styrene derivatives. Of these, (meth) acrylic acid esters are preferred. Specific examples of the polymerizable monomer having no acidic group are shown below. In the following description, the n-functional monomer is a monomer having n olefinic double bonds (functional groups). Examples of the acidic group-free polymerizable monomer include monofunctional, bifunctional, and trifunctional or higher functional polymerizable monomers. The monofunctional polymerizable monomer having no acidic group is hereinafter simply referred to as "monofunctional polymerizable monomer", and the bifunctional polymerizable monomer having no acidic group is simply referred to as "monofunctional polymerizable monomer". The "bifunctional polymerizable monomer" may be used, and the trifunctional or higher functional monomer having no acidic group may be simply referred to as a "polyfunctional polymerizable monomer".

<Polymeric monomer containing no acidic group; Monofunctional polymerizable monomer>
Examples of the monofunctional polymerizable monomer include the following compounds. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth). ) Acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6- Hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, propylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, erythritol mono (meth) acrylate, N-methylol (meth) acrylamide, N-hydroxy Ethyl (meth) acrylamide, N, N- (dihydroxyethyl) (meth) acrylamide and the like.

<Polymeric monomer containing no acidic group; Bifunctional polymerizable monomer>
Examples of the bifunctional polymerizable monomer include the following compounds. Specifically, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, 2,2-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2 -Bis [4- (meth) acryloyloxypolyethoxyphenyl] propane, 2,2-bis [4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl] propane, 1,2-bis [3- (Meta) acryloyloxy-2-hydroxypropoxy] ethane, pentaerythritol di (meth) acrylate, 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, [2,2,4-trimethylhexamethylenebis] (2-Carbamoyloxyethyl)] Dimethacrylate and the like.

<Polyfunctional polymerizable monomer containing no acidic group; Polyfunctional polymerizable monomer>
Examples of the polyfunctional polymerizable monomer include the following compounds. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, N, N'-(2,2) 4-trimethylhexamethylene) Bis [2- (aminocarboxy) propan-1,3-diol] tetramethacrylate, 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptan And so on.

The acidic group-free polymerizable monomers described above can be appropriately combined and used depending on the intended use of the dental composition. These acidic group-free polymerizable monomers are used alone or in combination of two or more. When a plurality of types are used, the reference compounding amount is the total amount thereof.

<Amount of acidic group-free polymerizable monomer>
In the dental composition of the present embodiment, an appropriate amount of the acidic group-free polymerizable monomer can be used as needed depending on the use of the dental composition and the like. When the acidic group-free polymerizable monomer is blended with the dental composition of the present embodiment, the acidic group-free polymerizable monomer is blended with 100 parts by mass of the (A) silane coupling agent. The amount is preferably 1 part by mass to 90000 parts by mass, and preferably 10 parts by mass to 50,000 parts by mass. The optimum blending amount of the acidic group-free polymerizable monomer may be appropriately determined according to the intended use of the dental composition.

Further, when the acidic group-free polymerizable monomer is blended in the dental composition of the present embodiment, a monofunctional polymerizable monomer or a bifunctional polymerizable monomer is used depending on the use of the dental composition. , And polyfunctional polymerizable monomers are preferably used in combination as appropriate.

<Filler>
If necessary, a filler may be further added to the dental composition of the present embodiment. As the filler, known organic fillers and inorganic fillers can be appropriately used.

Specific examples of organic fillers include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, ethylmethacrylate-butylmethacrylate copolymer, methylmethacrylate-trimethylolpropanetrimethacrylate copolymer, polyvinylchloride, and the like. Examples thereof include polystyrene, chlorinated polyethylene, nylon, polysulfone, polyether sulfone, and polycarbonate. In addition, these organic fillers do not contain an acidic group.

Specific examples of inorganic fillers include quartz, amorphous silica, silica zirconia, clay, aluminum oxide, talc, mica, kaolin, glass, barium sulfate, zirconium oxide, titanium oxide, silicon nitride, aluminum nitride, titanium nitride, and carbide. Examples thereof include silicon, boron carbide, calcium carbonate, hydroxyapatite and calcium phosphate.

When an inorganic filler (untreated inorganic filler) that has not been subjected to any surface treatment is blended in the dental composition of the present embodiment, the (A) silane coupling agent contained in the uniform composition is untreated. Reacts with inorganic filler and is consumed. Therefore, when the inorganic filler is blended in the dental composition of the present embodiment, it is preferable to use a surface-treated inorganic filler in which the untreated inorganic filler is surface-treated with a surface treatment agent. Further, when the untreated inorganic filler is blended in the dental composition of the present embodiment, the blending amount of the untreated inorganic filler is preferably kept in a small amount. Examples of the surface treatment agent used for the surface treatment of the untreated inorganic filler include known surface treatment agents such as a silane coupling agent. The silane coupling agent used as the surface treatment agent for the untreated inorganic filler does not function as the (A) silane coupling agent contained in the uniform composition because it reacts irreversibly with the surface of the untreated inorganic filler. ..

Further, when the (C1) acidic group-containing polymerizable monomer or acidic group-free polymerizable monomer is blended in the dental composition of the present embodiment, it is preferable to use a surface-treated inorganic filler. In this case, it becomes easy to improve the compatibility between these polymerizable monomers and the surface-treated inorganic filler, and to improve the mechanical strength and water resistance. The surface treatment method of the untreated inorganic filler may be a known method. The surface treatment agent includes methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, and vinyltris (β-). Methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyl Preferably, trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane and the like are preferable. Used.

The filler can be used alone or in combination of two or more types. When two or more types are used, the reference blending amount is the total amount thereof.

When the filler is blended in the dental composition of the present embodiment, the blending amount of the filler with respect to 100 parts by mass of the (A) silane coupling agent is preferably 1 part by mass to 50,000 parts by mass, and 10 parts by mass to 30,000 parts by mass. It is preferably a part. The optimum blending amount of the filler may be appropriately determined according to the use of the dental composition of the present embodiment.

<Photopolymerization initiator>
The dental composition of the present embodiment is selected from (C1) an acidic group-containing polymerizable monomer, an acidic group-free polymerizable monomer, and (A) a silane coupling agent containing a radically polymerizable group. If it contains at least one polymerizable monomer component, a photopolymerization initiator may be further used, if necessary. As the photopolymerization initiator, a photosensitizer that generates radicals by light irradiation can be used. Examples of photosensitizers for ultraviolet rays include benzoin compounds such as benzoin, benzoin methyl ether and benzoin ethyl ether, benzophenone compounds such as acetoinbenzophenone, p-chlorobenzophenone and p-methoxybenzophenone, thioxanthone, 2- Thioxanthone compounds such as chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc., 2,4,6-trimethyl Benzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) Phosphonate, acylphosphine oxides such as 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 3,3'-carbonylbis (7-diethylamino) coumarin, 3- (4-methoxybenzoyl) coumarin, 3-chenoyl coumarin Cumarins such as 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) ) -S-Triazine and other halomethyl group-substituted-s-triazine derivatives. In addition, a photosensitizer that initiates polymerization with visible light is preferably used because it does not require ultraviolet rays that are harmful to the human body. Examples of these are α such as benzyl, camphorquinone, α-naphthyl, acetnaphthene, p, p'-dimethoxybenzyl, p, p'-dictorenquinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, naphthoquinone and the like. − Examples include diketones. Preferably, camphorquinone is used.

These photosensitizers (photopolymerization initiators) can be used alone or in combination of two or more. When two or more types are used, the reference blending amount is the total amount thereof.

It is also preferable to use the photosensitizer in combination with a photopolymerization accelerator. In particular, when tertiary amines are used as a photopolymerization accelerator, it is more preferable to use a compound in which an aromatic group is directly substituted with a nitrogen atom. Examples of the photopolymerization accelerator include Ν, Ν-dimethylaniline, Ν, Ν-diethylaniline, Ν, Ν-di-n-butylaniline, Ν, Ν-dibenzylaniline, Ν, Ν-dimethyl-p-toluidine, Ν, Ν-dimethyl-m-toluidine, Ν, Ν-diethyl-p-toluidine, p-bromo-Ν, Ν dimethylaniline, m-chloro Ν, Ν-dimethylaniline, p-dimethylaminobensaldehyde, p- Dimethylaminoacetophenone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid aminoester, Ν, Ν-dimethylanthranic acid methyl ester, Ν, Ν-dihydroxyethylaniline, Ν, Ν- Dihydroxyethyl-p-toluidine, p-dimethylaminostyrene, Ν, Ν-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, Ν, Ν-dimethyl-α-naphthylamine, Ν, Ν-dimethyl-β-naphthylamine And so on. At least one of these photopolymerization accelerators can be selected and used, and two or more of these photopolymerization accelerators can be mixed and used.

These photopolymerization accelerators can be used alone or in combination of two or more. When two or more types are used, the reference blending amount is the total amount thereof.

The amount of the photopolymerization initiator and the photopolymerization accelerator to be blended in the dental composition of the present embodiment containing the polymerization initiator component can be appropriately determined. Usually, it is preferable to use an effective amount of the photopolymerization initiator and the photopolymerization accelerator. The blending amount of the photopolymerization initiator is 0.001 part by mass to 30 parts by mass when the total amount of the polymerizable monomer component blended in the dental composition of the present embodiment is 100 parts by mass. It is preferably 0.1 part by mass to 10 parts by mass, and more preferably 0.1 part by mass. The blending amount of the photopolymerization accelerator is preferably 0.001 part by mass to 30 parts by mass, preferably 0.1 part by mass to 10 parts by mass, when the total amount of the polymerizable monomer component is 100 parts by mass. Is more preferable.

<Chemical polymerization initiator>
The dental composition of the present embodiment is selected from (C1) an acidic group-containing polymerizable monomer, an acidic group-free polymerizable monomer, and (A) a silane coupling agent containing a radically polymerizable group. If it contains at least one polymerizable monomer component, a chemical polymerization initiator may be further used if necessary. As the chemical polymerization initiator, any known chemical polymerization initiator can be used without limitation. Examples of such a chemical polymerization initiator include a combination of organic peroxides and amines, a combination of organic peroxides, amines and sulfates, a combination of acidic compounds and arylborate compounds, and a fourth cycle transition metal. Examples thereof include a combination of a compound and an organic peroxide, a combination of an organic peroxide and a thiourea derivative, a chemical polymerization initiator such as barbituric acid and an alkylboran.

Examples of organic peroxides include various peroxides classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, peroxyesters, diacyl peroxides, and peroxydicarbonates. These can be used alone or in combination of two or more.

As the amines, secondary or tertiary amines are preferable, and specific examples thereof include N-methylaniline, N-methyl-p-toluidine and the like as secondary amines. N, N-Dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl. -P-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -Dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amylester, N, N-dihydroxyethyl-p-toluidine, 4-dimethylaminopyridine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N- Examples thereof include diethylaminoethyl (meth) acrylate and 2,2'-(n-butylimino) diethanol. These can be used alone or in combination of two or more.

As the aryl borate compound, a known compound can be used as long as it has at least one boron-aryl bond in one molecule, but it has high storage stability, is easy to handle, and can be obtained. Arylborate compounds having four boron-aryl bonds in one molecule are most preferred because of their ease of use. Specific examples of the arylborate compound having four boron-aryl bonds in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis (3,5-bistrifluoro). Methyl) phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (M-Nitrophenyl) Boron, Tetrax (p-butylphenyl) Boron, Tetrax (m-Butylphenyl) Boron, Tetrax (p-Butyloxyphenyl) Boron, Tetrax (m-Butyloxyphenyl) Boron, Tetrax (p-) Examples thereof include salts of boron compounds such as octyloxyphenyl) boron and tetrakis (m-octyloxyphenyl) boron. As the cation forming a salt with the boron compound, a metal ion, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion can be used. it can. These can be used alone or in combination of two or more.

As the thiourea derivative, a compound having a thiourea skeleton can be used without particular limitation, and a thiourea compound and a mercaptobenzimidazole compound described later are included, and can be appropriately selected depending on the intended purpose. For example, the thiourea compound includes ethylene thiourea, N, N'-dimethylthiourea, 1- (2-pyridyl) -2-thiourea, 1- (2-tetrahydrofurfuryl) -2-thiourea, 1-. Examples include acetyl-2-thiourea. Examples of the mercaptobenzimidazole compound include 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzoimidazole, 2-mercapto-5-ethoxybenzoimidazole, 2-mercapto-5-methylbenzimidazole, and 2-mercapto-5-. Examples thereof include ethylbenzimidazole. These can be used alone or in combination of two or more.

In the 4th period transition metal compound, the 4th period transition metal is a metal element of groups 3 to 12 of the 4th period of the periodic table, and specifically, scandium (Sc), titanium (Ti), vanadium ( V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn). Each of these transition metal elements can have a plurality of valences, but those having a valence that can exist stably, for example, Sc (III), Ti (IV), V (III to V), Cr (II, Compounds of III, VI), Mn (II-VII), Fe (II, III), Co (II, III), Ni (II), Cu (I, II), Zn (II) are at least organic peroxides. It is used as a chemical polymerization initiator in combination with a compound.

Specific examples of such a fourth period transition metal compound include scandium iodide (III), titanium chloride (IV), titanium (IV) tetraisopropoxide, divanadium tetraoxide (IV), and vanadium acetylacetonate oxide. (IV), vanazil oxalate (IV), vanadil sulfate (IV), oxobis (1-phenyl-1,3-butandionate) vanadium (IV), bis (maltlate) oxovanadium (IV), vanadium pentoxide (IV) V), chromium chloride (III), chromium acid (VI), chromate (VI), manganese acetate (II), iron acetate (II), iron acetate (III), cobalt acetate (II), cobalt naphthenate (V) II), nickel chloride (II), copper (I) chloride, copper (I) bromide, copper (II) chloride, copper (II) acetate, copper (II) sulfate, copper (II) acetylacetone, zinc acetate (II) ), Etc., which can be used alone or in combination of two or more.

When a chemical polymerization initiator is used for polymerization curing of the dental composition of the present embodiment containing a polymerization initiator component, at least one of the plurality of types of components constituting the chemical polymerization initiator (the first component). One component) is incorporated into the dental composition of the present embodiment. In addition, among all the components constituting the chemical polymerization initiator, the remaining type of component (second component) is another dental composition different from the dental composition of the present embodiment (hereinafter, "combined dentistry"). It may be referred to as "composition"). The blending amount of the first component to be blended in the dental composition of the present embodiment containing the polymerization initiator component can be appropriately determined according to the type of the chemical polymerization initiator to be used and the like. Generally, it is preferable to use effective amounts of the first and second components. The blending amount of the first component constituting a part of the chemical polymerization initiator is 0.001 mass by mass when the total amount of the polymerizable monomer component blended in the dental composition of the present embodiment is 100 parts by mass. It is preferably parts to 30 parts by mass, and more preferably 0.1 parts by mass to 10 parts by mass. As a combination of the composition constituting the first component and the composition constituting the second component, when both are present in a separated state, a stable state is maintained and the two are contacted and mixed. The combination that reacts when this is done is appropriately selected.

Examples of the combined dental composition in which the second component constituting the balance of the chemical polymerization initiator is blended include a dental bonding material, a composite resin, a compomer, a resin core, a resin cement, and a resin-reinforced glass ionomer cement. Examples include resin for denture base. Therefore, when the dental composition of the present embodiment containing the first component and the polymerizable monomer component is polymerized and cured, the dental composition and the combined dental composition are used in contact with or mixed with each other.

<Polymerization inhibitor>
If necessary, a known polymerization inhibitor that can be used for general dental materials can be added to the dental composition of the present embodiment containing a polymerization initiator component and a polymerizable monomer component. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene and the like. At least one of these polymerization inhibitors can be selected and used, and two or more of these polymerization inhibitors can be mixed and used.

The polymerization inhibitor may be used alone or in combination of two or more kinds. When two or more types are used, the reference blending amount is the total amount thereof.

The blending amount of the polymerization inhibitor is preferably 0.0001 part by mass to 10 parts by mass when the total amount of the polymerizable monomer component contained in the dental composition is 100 parts by mass.

<Container>
In the dental composition package of the present embodiment, as the container for accommodating the dental composition of the present embodiment, which is the material to be packaged, a container generally used conventionally can be used. Examples of such a container include bottles, syringes, packaging bags and the like. The material of the container is not particularly limited as long as it is not a material that may react with the (A) silane coupling agent such as glass, but from the viewpoint of usability and airtightness, polyethylene, polypropylene, polyvinyl alcohol, ethylene- It is preferably a synthetic resin such as a vinyl alcohol copolymer. When the dental composition of the present embodiment contains a photopolymerization initiator, it is necessary to use a light-shielding container as the container.

<Manufacturing method of dental composition packaging>
The method for producing a dental composition package of the present embodiment includes a dental composition preparation step and a filling step. In the dental composition preparation step, (A) a silane coupling agent: 100 parts by mass, (B) a water-soluble fluoride salt: a compounding amount in terms of parts by mass when the formula (1) is satisfied, and (C) acidity. All raw material components including compound: 1 part by mass or more and 10000 parts by mass or less, (D) organic solvent: 10 parts by mass or more and 90000 parts by mass or less, and (E) water: 10 parts by mass or more and 2000 parts by mass or less. Mix. Here, the mixing treatment is carried out until the respective raw material components are uniformly and sufficiently mixed. This prepares a dental composition containing the uniform composition. When preparing the dental composition, all the raw materials may be mixed at once. When (B) the solubility of the water-soluble fluoride salt in water is small, the first adjustment step of preparing an aqueous solution in which (B) the water-soluble fluoride salt and (E) water are mixed, and this aqueous solution , It is preferable to prepare a dental composition through a second adjustment step of mixing the remaining raw material components. Further, when preparing a dental composition containing a photopolymerization initiator, the dental composition preparation step is preferably carried out in an environment in which light having a wavelength at which the initiation reaction of the photopolymerization initiator occurs is cut off.

The filling step is a step of filling the container with the dental composition prepared in the dental composition preparation step. When the dental composition contains a photopolymerization initiator, it is preferable to carry out the filling step in an environment in which light having a wavelength at which the initiation reaction of the photopolymerization initiator occurs is cut off.

<Preferable use of dental composition (adhesive body)>
The dental composition of the present embodiment can be used for bonding various adherends. Materials constituting such an object to be adhered include zirconia ceramics, ceramics such as silica-based ceramics (porcelain, etc.), dentin (dental dentin, enamel), iron, nickel, chromium, cobalt, tin, aluminum, and the like. A cured resin (hard resin tooth, hybrid resin) containing a base metal containing copper, titanium or the like as a main component, a noble metal containing gold, platinum, palladium, silver or the like as a main component, and a filler such as silica particles or silica-zirconia particles. , CAD / CAM resin block) and other various dental materials.

Among such applications for bonding to an object to be adhered, the dental composition of the present embodiment is particularly excellent in adhesiveness to a cured resin body containing ceramics and silica-based particles. Therefore, the dental composition of the present embodiment is preferably used as a ceramic primer and a multipurpose adhesive.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.

1. 1. Abbreviations for substances The abbreviations for substances used in Examples and Comparative Examples will be described below.

<Silane coupling agent>
<1> (A) Silane Coupling Agent-MPTES: γ-methacryloxypropyltriethoxysisilane-MPTIPS: γ-methacryloxypropyltriisopropoxysilane-MMBSS: (methacryloxymethyl) bis (trimethylsiloxy) methylsilane-MPTSS : Methacryloxypropyltris (vinyldimethylsiloxy) silane / BMPTSS: 1,3-bis (3-methacryloxypropyl) tetrakis (trimethylsiloxy) disiloxane <2> (A) Other silane couplings other than silane coupling agents Agent ・ MPS: γ-methacryloxypropyltrimethoxysilane

<Fluorine compound>
<1> (B) Water-soluble fluoride salt, NaF: Sodium fluoride, KF: Potassium fluoride, CsF: Cesium fluoride, TBAF: Tetra-n-butylammonium fluoride <2> (B) Water-soluble fluoride Other Fluoride Compounds Other Than Salts ・ HF: Hydrofluoric Acid ・ TBABF: Tetra-n-butylammonium Difluoride ・ TBATF: Tetra-n-butylammonium Trifluoride ・ FASG: Fluoroaluminosilicate glass powder ( Tokuso Ionomer, manufactured by Tokuyama Co., Ltd.) is crushed to an average particle size of 0.5 μm using a wet continuous ball mill (New My Mill, manufactured by Mitsui Mine Co., Ltd.).

<(C) Acid compound>
<(C1) Acidic group-containing polymerizable monomer>
・ MDP: 10-methacryloyloxydecyldihydrogenphosphate ・ PM2: bis (2-methacryloyloxyethyl) acid phosphate

<Polymeric monomer containing no acidic group>
BisGMA: 2.2'-bis [4- (2-hydroxy-3-methacrylicoxypropoxy) phenyl] propane · 3G: triethylene glycol dimethacrylate · HEMA: 2-hydroxyethyl methacrylate

<Other ingredients>
・ CQ: Camphorquinone.
DMBE: Ethyl 4-dimethylaminobenzoate.

2. 2. ¹⁹ F-NMR measurement (NMR spectrum ratio)
The fluorine compounds used in the dental compositions of each example and comparative example were observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm by ¹⁹ F-NMR measurement. The ratio of the total integrated values of the spectra to be obtained (NMR spectrum ratio) was determined. The details of the measurement conditions of ¹⁹ F-NMR will be described below.

After 0.01 g of the fluorine compound used in each Example and each Comparative Example was dissolved in 1 g of heavy water, the ¹⁹ F-NMR spectrum was measured under the following conditions. FASG does not dissolve in the above mixing ratio. Therefore, the filtrate obtained by mixing the FASG collected in appropriate amounts with heavy water and then stirring at room temperature for 24 hours and filtering the insoluble components with a filter having a mesh size of 0.2 μm was used for the measurement. ..
Measuring device: Nuclear magnetic resonance device (400MHz FT-NMR) JNM-ECA4002 Made by JEOL RESONANCE Co., Ltd. Measuring method: Single pulse method Observation nucleus: 19F
Sample rotation speed: 15 Hz
Measurement temperature: 22 ° C
Resonance frequency: 376.17 MHz
Flip nucleus: 45 °
90 ° pulse width: 8 us
Waiting time: 5s
Accumulation number: 64
Spectral width: 250ppm-250ppm
Reference substance: Trifluorotoluene C ₆ H ₅ CF ₃ (external standard: -64 ppm)
Sample tube outer diameter: 5 mm

The NMR spectrum ratios of various fluorine compounds are shown together with the peak chemical shift and the ratio of the integrated values of each spectrum.

3. 3. Preparation of Dental Compositions of Examples and Comparative Examples Examples 1 to 20 are obtained by sufficiently mixing all the components constituting the dental composition at the blending ratios shown in Tables 2 to 5 until they become uniform. And the dental compositions of Comparative Examples 1 to 15 were obtained. Tables 2 and 3 show the blending ratio (mass%) of each component when the total amount of the dental composition is 100% by mass in each Example (Table 2) and each Comparative Example (Table 3). did. Tables 2 and 3 also show the Bm / Am ratio.

On the other hand, Tables 4 and 5 show the compounding ratio (parts by mass) of each component per 100 parts by mass of the silane coupling agent in each Example (Table 4) and each Comparative Example (Table 5). It was.

When the dental compositions of Examples and Comparative Examples immediately after preparation were visually observed, it was confirmed that all the components were uniformly mixed and dissolved in the dental compositions other than Comparative Example 15. .. Further, when the dental compositions of the Examples and Comparative Examples immediately after the preparation were left to stand in a room temperature environment for one month and then visually observed again, no phase separation or precipitates were confirmed, and the same as immediately after the preparation. It was confirmed that all the components were uniformly mixed and dissolved. From these visual observation results, it was found that the dental compositions of Examples 1 to 20 and Comparative Examples 1 to 14 were composed only of the uniform composition. On the other hand, when the dental composition of Comparative Example 15 immediately after preparation was visually observed, FASG precipitated without being dissolved. Further, when the weight of the precipitate (solid content) obtained by filtering the dental composition of Comparative Example 15 immediately after preparation and after leaving it in a normal temperature environment for 1 month, the weight of the precipitate was measured. It was confirmed that the amount was consistent with the amount of FASG.

4. Evaluation of Adhesive Strength Using the dental compositions of each Example and Comparative Example, the adhesive strength was evaluated by the procedure described below.

First, as an adherend, "Noritake Super Porcelain AAA" (manufactured by Noritake, 15 mm in length × 15 mm in width × 3 mm in thickness), which is a dental ceramic (so-called porcelain) made of silica-based crystallized glass, was prepared. Next, one side of the adherend was polished with # 800 water resistant abrasive paper. Then, a double-sided tape having a hole with a diameter of 3 mm was attached to the polished surface of the adherend. Subsequently, the dental compositions of each Example and each Comparative Example were applied to the adhesive surface of the polished surface exposed from the holes of the double-sided tape with a microbrush. Then, the dental composition applied to the adhesive surface was dried by air blowing for 5 seconds.

Subsequently, in Examples 3 to 20 and Comparative Examples 3 to 15 to which the photopolymerization initiator was added, the dental composition was irradiated with light for 10 seconds with a visible light irradiator (Power Light, manufactured by Tokuyama Dental Co., Ltd.). It was cured.

Next, a paraffin wax having a thickness of 0.5 mm provided with a hole having a diameter of 8 mm is attached to the adhesive surface coated with the dental composition so that the hole of the paraffin wax and the hole of the double-sided tape are concentric circles. A simulated cavity was prepared. This simulated tooth cavity is filled with a dental composite resin (Esterite Σ Quick, manufactured by Tokuyama Dental Co., Ltd.), lightly pressed with a polyester film, and then lighted using a visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Photocuring was performed by irradiation for 10 seconds. Then, a pre-polished round bar made of SUS304 (diameter 8 mm, height 18 mm) was bonded using resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.). Finally, a sample for measuring the adhesive strength was obtained by immersing the simulated tooth cavity to which the round bar was adhered via the composite resin and the resin cement in water at 37 ° C. for 24 hours. The composite resin used (Esterite Σ Quick) is a photopolymerizable composition containing camphorquinone and an amine compound. The tensile adhesive strength of these samples for measuring the adhesive strength was measured using an autograph (crosshead speed 2 mm / min) manufactured by Shimadzu Corporation. For each Example and Comparative Example, the measured values of the four samples were averaged and used as the measurement result.

Table 6 shows the evaluation results of the following items (a)-(d).
(A) Measurement result of adhesive strength of sample obtained by applying the dental composition immediately after preparation to the adhesive surface ("initial" adhesive strength)
(B) The adhesive strength of the sample obtained by applying the dental composition immediately after preparation to the adhesive surface after further storing it in a constant temperature bath at 50 ° C. for 3 weeks (“50 ° C.”). Adhesive strength after storage for 3 weeks)
(C) The adhesive strength of the sample obtained by applying the dental composition immediately after preparation to the adhesive surface after further storing it in a constant temperature bath at 50 ° C. for 6 weeks (“50 ° C.”). Adhesive strength after 6 weeks of storage)
(D) Adhesive strength at "50 ° C for 6 weeks" / "Initial" adhesive strength (%) ("Adhesive strength retention rate")

<About the evaluation results shown in Table 6>
The adhesion test results of Examples 1 to 20 were good at the initial stage, after storage at 50 ° C. for 3 weeks, and after storage at 50 ° C. for 6 weeks.

On the other hand, the dental compositions of Comparative Examples 1, 2, 4, 5, and 6 do not contain (B) a water-soluble fluoride salt at all. Therefore, it is presumed that hydrolysis and dehydration condensation of the (A) silane coupling agent occur during storage, and the adhesive strength after storage is significantly reduced with respect to the initial stage. Comparative Examples 11, 12, 13, and 15 use other fluorine compounds different from (B) the water-soluble fluoride salt. Therefore, it is presumed that the effect of the addition of the fluorine compound was not sufficiently produced, and the adhesive strength after storage was significantly reduced compared to the initial stage. Further, in Comparative Example 15, it is presumed that the silanol group of the silane coupling agent was bonded to FASG itself, and the adhesive strength was significantly reduced.

In Comparative Example 7, the amount of (B) water-soluble fluoride salt compounded was small. Therefore, it is presumed that the effect of adding the (B) water-soluble fluoride salt was not sufficiently produced, and the adhesive strength after storage was significantly reduced with respect to the initial stage. In Comparative Example 10, the amount of (B) water-soluble fluoride salt compounded is too large. Therefore, it is presumed that (B) the water-soluble fluoride salt acts as an inhibitor of adhesion and the initial adhesive strength is lowered. Further, in Comparative Example 10, the adhesive strength is greatly reduced even after storage. It is presumed that the reason for this is that (B) most of the hydrolyzable groups were fluorinated by the water-soluble fluoride salt, so that the hydrolyzable groups could not sufficiently participate in the adhesion.

In Comparative Example 14, another silane coupling agent different from the (A) silane coupling agent is used. In the silane coupling agent used in Comparative Example 14, all hydrolyzable groups are highly hydrolyzable methoxy groups. Therefore, it is presumed that the effect of sufficiently stabilizing the dental composition was not obtained, and the adhesive strength after storage was greatly reduced.

Comparative Examples 3, 8 and 9 do not contain (A) a silane coupling agent, (C) an acidic compound, and (E) water, respectively. Therefore, it is presumed that sufficient adhesive strength could not be obtained.

5. Existence of Dental Composition The ¹⁹ F-NMR and ²⁹ Si-NMR measurements described below are performed on a sample left at a temperature of 25 ° C. for 1 day after preparing the dental compositions of Examples 1, 5, 9 and 10. And each NMR spectrum was confirmed. As a result, from these NMR spectra, a peak derived from Si-F ( ¹⁹ F-NMR: -157 ppm, ²⁹ Si-NMR: 36 ppm), a peak derived from Si-OH ( ²⁹ Si-NMR: 14 ppm), and free fluorine ions A peak of origin ( ¹⁹ F-NMR: -135 ppm) was confirmed.

< ¹⁹ F-NMR measurement>
After dissolving 0.5 g of the dental composition in 0.5 g of deuterated acetone, the ¹⁹ F-NMR spectrum was measured under the following conditions.
Measuring device: Nuclear magnetic resonance device (400MHz FT-NMR) JNM-ECA4002 Made by JEOL RESONANCE Co., Ltd. Measuring method: Single pulse method Observation nucleus: 19F
Sample rotation speed: 15 Hz
Measurement temperature: 22 ° C
Resonance frequency: 376.17 MHz
Flip nucleus: 45 °
90 ° pulse width: 8 us
Waiting time: 5s
Accumulation number: 64
Spectral width: 250ppm-250ppm
Reference substance: Trifluorotoluene C6H5CF3 (external standard: -64 ppm)
Sample tube outer diameter: 5 mm

< ²⁹ Si-NMR measurement>
The dental composition was measured as a stock solution under the following conditions.
Measuring device: Nuclear magnetic resonance device (400MHz FT-NMR) JNM-ECA4002 Made by JEOL RESONANCE Co., Ltd. Measuring method: Single pulse method Observation nucleus: 29Si
Sample rotation speed: 15 Hz
Measurement temperature: 22 ° C
Resonance frequency: 79.42MHz
Flip nucleus: 30 °
90 ° pulse width: 55 us
Waiting time: 20s
Accumulation number: 2500
Spectral width: 250ppm-250ppm
Reference substance: Tetramethylsilane Si (CH3) 4 (external standard: 0 ppm)
Sample tube outer diameter: 10 mm

Claims (7)

A dental composition containing a uniform composition and a container containing the dental composition.
<I> The uniform composition
(A) Silane coupling agent: 100 parts by mass and
(B) Water-soluble fluoride salt and
(C) Acidic compound: 1 part by mass or more and 10000 parts by mass or less
(D) Organic solvent: 10 parts by mass or more and 90000 parts by mass or less,
(E) Water: 10 parts by mass or more and 2000 parts by mass or less,
Consists of a composition in which all components including
<Ii> The (A) silane coupling agent is
(A) A silicon atom in which a polymerizable group and one to three hydrolyzable groups are bonded in the molecule (excluding the silicon atom represented as "Si" in the following structural formula (1s)). Including and
(B) The hydrolyzable group is selected from the group consisting of (b1) an alkoxy group having 1 to 30 carbon atoms, (b2) a substituted siloxy group represented by the following structural formula (1s), and (b3) a hydrogen atom. Is the basis for being
(C) When three (b1) alkoxy groups as the hydrolyzable groups are bonded to the silicon atom, the carbon number of these three (b1) alkoxy groups is 2 or more and 30 or less.
It is a silicon compound

[In the structural formula (1s), R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively. ]
<Iii> In ¹⁹ F-NMR when the water-soluble fluoride salt (B) was dissolved in water, it was observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm. The total ratio of the integrated values of the spectra is 70% or more, and
<Iv> The content of the water-soluble fluoride salt (B) contained in the uniform composition is within the range satisfying the following formula (1).
Dental composition packaging characterized by that.
-Equation (1) 0.001 ≤ Bm / Am ≤ 6
[In the formula (1), Am means the total number of moles (mol) of the hydrolyzable group contained in 100 parts by mass of the silane coupling agent of the (A), and Bm is the (B). It means the total number of moles (mol) of fluorine atoms derived from a water-soluble fluoride salt. ] The (A) silane coupling agent is at least one silane coupling agent selected from the group consisting of the following first silane coupling agent, the following second silane coupling agent, and the following third silane coupling agent. The dental composition package according to claim 1, wherein the dental composition package comprises.
[First silane coupling agent]: A silane coupling agent composed of a silicon compound represented by the following structural formula (1).

(In the structural formula (1),
V ¹¹ is a methyl group, or a hydrogen atom,
W ¹¹ is an oxygen atom or an imino group,
R ¹¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
Each of X ¹¹ , Y ¹¹ , and Z ¹¹ is a hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms in (b1), or the substituted siloxy represented by the structural formula (1s) in (b2). Is the basis
At least one of X ¹¹ , Y ¹¹ , and Z ¹¹ is a substituted siloxy group represented by the structural formula (1s) (b2). )
[Second silane coupling agent]: A silane coupling agent composed of a silicon compound represented by the following structural formula (2).

(In the structural formula (2),
V ²¹ is a methyl group or a hydrogen atom.
W ²¹ is an oxygen atom or an imino group,
R ²¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
Each of X ²¹ and Z ²¹ is a hydrocarbon group having 1 to 30 carbon atoms, the alkoxy group having 1 to 30 carbon atoms (b1), or the substituted siloxy group represented by the structural formula (1s) (b2). .. )
[Third Silane Coupling Agent]: A silane coupling agent composed of a silicon compound represented by the following structural formula (3).

(In the structural formula (3),
V ³¹ is a methyl group or a hydrogen atom.
W ³¹ is an oxygen atom or an imino group,
R ³¹ is a divalent hydrocarbon group having 1 to 30 carbon atoms.
Each of X ³¹ , Y ³¹ , and Z ³¹ is independently a hydrocarbon group having 1 to 30 carbon atoms or the (b1) alkoxy group having 1 to 30 carbon atoms. However, at least one group selected from X ³¹ , Y ³¹ , and Z ³¹ is an alkoxy group having 2 to 5 carbon atoms. ) The dental composition package according to claim 1 or 2, wherein the (C) acidic compound contains (C1) an acidic group-containing polymerizable monomer. Claims 1 to 3 characterized in that the dental composition is any composition selected from the group consisting of a one-component dental adhesive composition and a one-component dental primer composition. The dental composition package according to any one. The dental composition package according to any one of claims 1 to 4, wherein the dental composition comprises only the uniform composition. (A) Silane coupling agent: 100 parts by mass and
(B) Water-soluble fluoride salt: A blending amount in terms of parts by mass when the above formula (1) is satisfied, and
(C) Acidic compound: 1 part by mass or more and 10000 parts by mass or less
(D) Organic solvent: 10 parts by mass or more and 90000 parts by mass or less,
(E) Water: 10 parts by mass or more and 2000 parts by mass or less,
A dental composition preparation step of preparing the dental composition containing the uniform composition by mixing all the raw material components including
A filling step of filling the container with the dental composition and
The method for producing a dental composition package according to any one of claims 1 to 5, wherein the dental composition package comprises. Contains a homogeneous composition,
<I> The uniform composition
(A) Silane coupling agent: 100 parts by mass and
(B) Water-soluble fluoride salt and
(C) Acidic compound: 1 part by mass or more and 10000 parts by mass or less
(D) Organic solvent: 10 parts by mass or more and 90000 parts by mass or less,
(E) Water: 10 parts by mass or more and 2000 parts by mass or less,
Consists of a composition in which all components including
<Ii> The (A) silane coupling agent is
(A) A silicon atom in which a polymerizable group and one to three hydrolyzable groups are bonded in the molecule (excluding the silicon atom represented as "Si" in the following structural formula (1s)). Including and
(B) The hydrolyzable group is selected from the group consisting of (b1) an alkoxy group having 1 to 30 carbon atoms, (b2) a substituted siloxy group represented by the following structural formula (1s), and (b3) a hydrogen atom. Is the basis for being
(C) When three (b1) alkoxy groups as the hydrolyzable groups are bonded to the silicon atom, the carbon number of these three (b1) alkoxy groups is 2 or more and 30 or less.
It is a silicon compound

[In the structural formula (1s), R ¹² , R ¹³ , and R ¹⁴ are hydrocarbon groups having 1 to 30 carbon atoms or alkoxy groups having 1 to 30 carbon atoms, respectively. ]
<Iii> In ¹⁹ F-NMR when the water-soluble fluoride salt (B) was dissolved in water, it was observed at -110 ppm to -140 ppm with respect to the total integrated value of the entire spectrum observed at 250 ppm to -250 ppm. The total ratio of the integrated values of the spectra is 70% or more, and
<Iv> The content of the water-soluble fluoride salt (B) contained in the uniform composition is within the range satisfying the following formula (1).
A dental composition characterized by that.
-Equation (1) 0.001 ≤ Bm / Am ≤ 6
[In the formula (1), Am means the total number of moles (mol) of the hydrolyzable group contained in 100 parts by mass of the silane coupling agent of the (A), and Bm is the (B). It means the total number of moles (mol) of fluorine atoms derived from a water-soluble fluoride salt. ]