JP5279233B2 - Primer composition for surface treatment of cured dental prosthesis - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a primer composition for treating the surface of a dental prosthesis made of a resin cured product, which does not contain an amine component, does not have problems of smell and discoloration and effectively improves adhesiveness of the prosthesis made of the resin cured product to resin cement. <P>SOLUTION: The primer composition for treating the surface of the dental prosthesis made of the resin cured product comprises (A) a polymerizable monomer component containing &ge;5 mass% of an acidic group-containing polymerizable monomer, (B) a polyvalent metal ion, (C) a volatile organic solvent and (D) water. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a primer composition used for the surface treatment of a resin-cured prosthesis used in the field of dentistry, and more specifically, the resin-cured dental prosthesis is used as a tooth restoration part. The present invention relates to a primer composition used for filling or for restoring the resin-cured dental prosthesis itself.

  When a tooth has a defect due to caries or the like, and the defect is large, the tooth is repaired by a prosthesis such as an inlay, an onlay, or a crown. That is, a prosthesis having the shape of a tooth defect is formed at a technical laboratory or the like, and the dental prosthesis is bonded and fixed to the tooth defect using a paste-like adhesive called dental cement at a dental clinic. Is.

  Various types of prosthetics are known, such as those made of base metal alloys such as cobalt and chromium alloys, those made of noble metal alloys such as gold, silver and palladium alloys, and glass ceramics. Known are those made of ceramics and those made of cured resin obtained by curing a curable resin composition in which a large amount of inorganic filler is dispersed. Each has advantages and disadvantages, but recently, a prosthesis made of a cured resin that is particularly excellent in aesthetics and easy to mold tends to be widely used.

  By the way, as dental cement which is the above-mentioned adhesive, what is called a resin cement composed of a (meth) acrylate polymerizable monomer, an inorganic filler and a chemical polymerization initiator is widely used. Since such dental cement does not show sufficient adhesion directly to the above-mentioned prosthesis, after the surface of the prosthesis is treated with a primer, the dental prosthesis is used to remove the dental defect. It is to be fixed to. In addition, such a prosthesis is fixed to a tooth defect portion for a long period of time, and the prosthesis itself may be damaged due to breakage or the like, and the prosthesis may be repaired. In such a case, for example, the restoration of the prosthesis itself is performed by re-fixing the prosthesis that has been broken and dropped off to the defect using a resin cement. Surface treatment of the prosthesis is performed using the prepared primer.

  As the primer as described above, an appropriate type is used depending on the type of prosthesis. For example, as a primer used for a base metal alloy prosthesis, an acidic group-containing polymerizable monomer is used. Primers used for organic solvent solutions and precious metal alloy prostheses include organic solvent solutions of sulfur atom-containing polymerizable monomers such as thiouracil-based polymerizable monomers, ceramic prostheses and resin curing As a primer for a product prosthesis, an organic solvent solution containing a silane coupling agent and an acidic group-containing polymerizable monomer has been used.

  However, among the above-mentioned primers, those used for base metal alloy, noble metal alloy and ceramic prostheses sufficiently improve the adhesion to dental cement and the like. Regarding the primer used for the prosthesis, the effect of improving adhesiveness was insufficient. In other words, the primer used for the resin-made prosthesis has improved adhesion because silanol groups generated by hydrolysis of the silane coupling agent react with the silanol groups on the filler surface in the resin-cured product. The surface of the filler is covered with a cured resin, so that there are few reactive points between silanol groups, resulting in insufficient adhesion improvement. is there.

As an improvement of the drawbacks of such a cured resin-made prosthetic primer, the present applicant has previously described an acidic group-containing polymerizable monomer (A), an aromatic amine (B), and a volatile organic solvent ( A primer composition comprising C) was proposed (Patent Document 1). In such a primer composition, an aromatic amine reacts with an acidic group-containing polymerizable monomer to form a surfactant, and this surfactant improves the wettability between the cured resin and the resin cement. The adhesive force between the cured dental prosthesis and the resin cement can be effectively improved.
JP 2006-45094 A

  However, since the primer composition disclosed in Patent Document 1 described above contains a large amount of amine, there is a problem of odor, filling and fixing to the restoration part of the tooth of the resin-cured prosthesis, It is still unsatisfactory in that it gives the patient discomfort during the restoration of the prosthesis. There is also a problem of coloring due to an amine component, for example, a problem that the prosthesis is discolored. Furthermore, there is a problem that the aromatic amine and the acidic group-containing polymerizable monomer must be stored in separate packages.

Accordingly, an object of the present invention is to contain a resin-cured dental product that does not contain an amine component as an essential component, has no problems of odor and coloring, and can effectively improve the adhesion of the resin-cured product prosthesis to the resin cement. Another object of the present invention is to provide a primer composition for surface treatment of a prosthesis.
Another object of the present invention is to provide a one-component primer composition for surface treatment of a cured dental prosthesis that is stored in a single package and does not require troublesome operations such as two-component mixing.
Still another object of the present invention is to provide a primer kit that can be easily applied to any kind of dental prosthesis made of base metal, precious metal and ceramics, as well as surface treatment of hardened dental prosthesis. There is to do.

According to the present invention,
(A) a polymerizable monomer component containing 5% by mass or more of an acidic group-containing polymerizable monomer;
(B) a polyvalent metal ion;
(C) The boiling point at 760 mmHg is 100 ° C. or lower, and the vapor pressure at 20 ° C. is
A volatile organic solvent of 1.0 KPa or higher ;
(D) water;
A primer composition for treating a surface of a dental prosthesis made of a cured resin is provided.

In the primer composition of the present invention, preferred embodiments are as follows.
(1) The content of the polyvalent metal ion (B) is such that the polymerizable monomer component (A)
The amount is 1.0 to 7.0 meq per gram, and the volatile organic solvent (C) is contained in the range of 30 to 150 parts by mass per 100 parts by mass of the polymerizable monomer component (A). The water (D) is contained in an amount of 3 to 30 parts by mass per 100 parts by mass of the polymerizable monomer component (A), and the components are mixed to form one liquid. Stored in the package.
(2) The volatile organic solvent (C) is converted into the following formula (I):
α ≧ 20 · X (I)
In the formula, α is the polymerizable monomer component (A) of the volatile organic solvent (C).
It is a blending amount per 100 parts by mass,
X is a polyvalent metal ion (B) per 1 g of the polymerizable monomer component (A).
Is a number indicating the amount (meq) of
It must be contained in an amount that satisfies the conditions expressed by
(3) The polyvalent metal ion (B) is present by elution from the polyvalent metal ion-eluting filler.
(4) The polyvalent metal ion-eluting filler has an elution amount of polyvalent metal ions of 5.0 to 500 meq when 0.1 g of the filler is added to 10 ml of 10 wt% maleic acid aqueous solution and held at 23 ° C. for 24 hours. / G-filler.
(5) The polyvalent metal ion-eluting filler is a powder having an average particle size of 0.01 to 5 μm.
(6) The acidic group-containing polymerizable monomer in the polymerizable monomer component (A) is a polymerizable monomer containing a phosphate group.
(7) Furthermore, (E) 2-20 mass parts of polyvalent metal ion non-releasing inorganic filler is contained per 100 mass parts of said polymerizable monomer component (A).
(8) It further contains (F) a photopolymerization initiator.

According to the present invention, a package containing a resin-cured dental prosthesis surface treatment primer composition containing the components (A) to (D) in a predetermined amount ratio, and a sulfur atom-containing polymerizable monomer consists of a body and / or package compatible extension primer aid is accommodated to the silane coupling agent list consisting of organic solvents,
The volatile organic solvent is a volatile organic solvent having a boiling point at 760 mmHg of 100 ° C. or lower and a vapor pressure at 20 ° C. of 1.0 KPa or higher,
Dental prosthesis in which the sulfur atom-containing polymerizable monomer is at least one selected from the group consisting of a radical polymerizable compound that generates a mercapto group by tautomerism, a radical polymerizable disulfide compound, and a radical polymerizable thioether compound Primer kits are provided.

According to the primer composition of the present invention, it is possible to remarkably improve the adhesiveness with the resin cement by performing the surface treatment of the cured resin prosthesis using the primer composition, and as a result, the resin cement is used for the resin. The hardened prosthesis can be firmly bonded and fixed to the restoration part of the tooth, and even when the prosthesis itself is damaged, the prosthesis that has been broken and dropped using the resin cement is prosthetic. It becomes possible to re-fix to the deficient part. The reason why such an effect appears is not clearly elucidated, but the present inventors presume as follows.
That is, when this primer composition was applied to the surface of a dental prosthesis made of a cured resin, it penetrated into the surface portion of the prosthesis (cured resin), and at the same time, a resin cement was applied thereon. In some cases, the resin cement also has good affinity, and during the curing reaction of the resin cement, the polymerizable monomer component including the acidic group-containing polymerizable monomer is polymerized and cured. Further, in addition to this curing reaction, not only the ionic cross-linking of the polymer chain by the action of the acidic group derived from the acidic group-containing polymerizable monomer, water and polyvalent metal ions occurs, but also such an ionic cross-linked product. Has a hydrophilic ion binding part and a hydrophobic polymer chain part, so the affinity between the resin cement and the prosthesis is enhanced, and the penetration of the range cement into the cured resin (prosthesis) Enhanced. It is believed that such a synergistic effect of polymerization hardening and ionic cross-linking produces a strong adhesive force for both the dental prosthesis and the resin cement.

  In addition, the primer composition of the present invention does not contain an amine component as an essential component and does not cause any odor or coloring problem. Is also excellent.

  In the present invention, the amount of polyvalent metal ions can be easily adjusted to an appropriate concentration range by adjusting the amount of volatile organic solvent used. Is suppressed to a level where there is no problem, and can be stored for a long time in one package, and can be used as a one-component primer composition. In addition, since the polyvalent metal ions are diluted with a volatile organic solvent, the composition can be easily applied to the surface of the resin-cured prosthesis by air blowing after use. It can be volatilized and can be concentrated in a short time so that the ionic bond by the polyvalent metal ion becomes strong, and then the adhesion by radical polymerization and the ion of the polymerized acidic group-containing polymerizable monomer A synergistic effect with adhesion by cross-linking is surely exhibited, and a stable and high adhesive force improving effect is exhibited.

  Further, the one-component primer composition of the present invention is used as a primer for a prosthesis made of a cured resin, but contains an acidic group-containing polymerizable monomer component, so that a prosthesis made of a base metal alloy is used. In addition to exhibiting a relatively high adhesion improvement effect, if a sulfur atom-containing polymerizable monomer is added thereto, the adhesion improvement effect is significantly higher for base metal alloy and precious metal alloy prostheses. If a silane coupling agent is added, a high effect of improving adhesiveness with respect to a ceramic prosthesis is exhibited. Accordingly, an organic solvent solution containing a sulfur atom-containing polymerizable monomer and / or silane coupling agent as an active ingredient is packaged as a primer aid for compatibility extension, and the content of each component is within a predetermined range. The primer kit combined with the package containing the primer composition of the present invention adjusted to the above can be used for primer treatment of a prosthesis, regardless of the type of the prosthesis. That is, in this primer kit, the above-described primer composition of the present invention is used for a resin and base metal alloy prosthesis, and the present invention is used for a noble metal alloy or ceramic prosthesis. The primer composition may be used with a primer aid for expanding compatibility.

  The primer composition of the present invention used for the primer treatment (adhesion improvement treatment) of the resin-made prosthesis is composed of (A) a polymerizable monomer component, (B) a polyvalent metal ion, ( C) It contains a volatile organic solvent and (D) water, and (E) an inorganic filler and (F) a photopolymerization initiator are blended as necessary.

<Polymerizable monomer component (A)>
In the present invention, the polymerizable monomer component (A) (hereinafter simply referred to as “monomer component”) is used for imparting adhesiveness to the resin cured product or resin cement used as an adhesive. However, in order to increase the permeability to the cured resin and resin cement, 5% by mass or more of the polymerizable monomer component (A) is the acidic group-containing polymerizable monomer (A1). It is necessary to be. That is, when the amount of the acidic group-containing polymerizable monomer (A1) is small, the primer composition does not exhibit sufficient permeability to the cured resin or resin cement, and the prosthesis made of the cured resin. This is because it becomes difficult to firmly bond the resin cement to the object.

  In addition, the monomer component (A) may all be an acidic group-containing polymerizable monomer (A1), but the strength of the adhesive interface and the permeability to a cured resin product (prosthesis) or resin cement. In order to adjust and obtain more excellent adhesive strength and adhesion durability, it is preferable to further contain a polymerizable monomer (A2) having no acidic group.

  For example, the content ratio of the acidic group-containing polymerizable monomer (A1) in the monomer component (A) is preferably in the range of 5 to 80% by mass, particularly 20 to 70% by mass, and the balance is acidic. It may be a polymerizable monomer (A2) that does not contain a group. That is, if the blending amount of the acidic group-containing polymerizable monomer (A1) is small, the permeability of the resin cement to the resin cured product is lowered, and the adhesiveness to the range cured product, that is, the resin cured product prosthesis is lowered. Resulting in. Moreover, when there is too much this quantity, there exists a tendency for the intensity | strength of primer composition itself to fall, and there exists a tendency for adhesiveness to fall.

Acidic group-containing polymerizable monomer (A1):
In the present invention, the acidic group-containing polymerizable monomer (A1) 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. Can be used.

Examples of the acidic group that the monomer (A1) has in the molecule include the following.
Examples of acidic groups;

  Examples of the polymerizable unsaturated group in the monomer (A1) include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. Can be mentioned.

  In the present invention, as a specific example of the polymerizable monomer (A1) having an acidic group and a polymerizable unsaturated group as described above in the molecule, a compound represented by the following formula is representative. .

但し上記化合物中、Ｒ^１は水素原子またはメチル基を表す。 Representative examples of acidic group-containing polymerizable monomer (A1);

In the above compounds, R ¹ represents a hydrogen atom or a methyl group.

  In addition to the above compounds, vinyl phosphonic acids in which a phosphonic acid group is bonded directly to a vinyl group, acrylic acid, methacrylic acid, vinyl sulfonic acid, etc., are used as acidic group-containing polymerizable monomers (A1). Can do.

  The acidic group-containing polymerizable monomer (A1) exemplified above can be used alone or in admixture of two or more, and among them, a compound having an acid valence in the molecule of 2 or more. It is preferable to use (polybasic acid compound) from the viewpoint of enhancing ionic bonding with a polyvalent metal ion described later and obtaining strong adhesive strength. Such a polybasic acid compound may have two or more monovalent acid groups in the molecule, or may have at least one divalent or more acid group in the molecule. . However, when only such a polybasic acid compound is used as the acidic group-containing polymerizable monomer (A1), it is preferable from the viewpoint of improving the strength, but the storage stability in a one-component state tends to be slightly lowered. is there. Therefore, it is more preferable to use a polybasic acid compound in combination with an acidic compound having a monovalent acid valence in the molecule in order to achieve both adhesive strength and storage stability.

In addition, when the polybasic acid compound and the monovalent acidic compound are used in combination as the acidic group-containing polymerizable monomer (A1) as described above, any of the compounds has a phosphoric acid group (for example,
-O-P (= O) ( OH) 2, (- O-) is most preferred that those containing the _{2 P} (= O) OH, etc.). Since the system in which the acidic group-containing polymerizable monomer (A1) is used in such a combination exhibits high permeability to the resin cured product, high adhesive strength is obtained for the resin cured product, Furthermore, the thing with the favorable storage stability in 1 liquid state is obtained.

  Furthermore, from the viewpoint of curing speed, the acidic group-containing polymerizable monomer (A1) is preferably a compound having an acryloyl group, a methacryloyl group, an acrylamide group, or a methacrylamide group as a polymerizable unsaturated group. .

Polymerizable monomer (A2) not containing an acidic group:
The polymerizable monomer (A2) containing no acidic group that can be used in combination with the monomer (A1) does not contain an acidic group and has at least one polymerizable unsaturated group in the molecule. As long as the condition that it is satisfied, known compounds can be used without any limitation. Examples of the polymerizable unsaturated group possessed by the polymerizable monomer include the same ones as exemplified for the monomer (A1) described above, and in particular, an acryloyl group, a methacryloyl group, an acrylamide. Group, methacrylamide group is preferred.

  Typical examples of such a polymerizable monomer (A2) include the following (meth) acrylate monomers, which may be used alone or in combination of two or more. it can.

1. Mono (meth) acrylate monomers;
Methyl (meth) acrylate,
Ethyl (meth) acrylate,
Glycidyl (meth) acrylate,
2-cyanomethyl (meth) acrylate,
Benzyl (meth) acrylate,
Polyethylene glycol mono (meth) acrylate,
Allyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate,
Glycidyl (meth) acrylate,
3-hydroxypropyl (meth) acrylate,
Glyceryl mono (meth) acrylate,
2- (meth) acryloxyethyl acetyl acetate and the like.

2. Polyfunctional (meth) acrylate monomers;
Ethylene glycol di (meth) acrylate,
Diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate,
Nonaethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate,
Dipropylene glycol di (meth) acrylate,
2,2′-bis [4- (meth) acryloyloxyethoxyphenyl] propane,
2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane,
2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane,
1,4-butanediol di (meth) acrylate,
1,6-hexanediol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate,
Urethane (meth) acrylate,
Epoxy (meth) acrylate and the like.

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

  In the present invention, when a highly hydrophobic polymerizable monomer is used as the polymerizable monomer (A2), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. It is preferable to use an amphiphilic monomer. By using such an amphiphilic monomer in combination, it is possible to prevent separation of water, which is an essential component of the primer composition of the present invention, to ensure uniformity of the composition, and to stably provide high adhesive strength. Because it can be obtained.

<Multivalent metal ion (B)>
It is important that the primer composition of the present invention contains a polyvalent metal ion as the component (B). In other words, the polyvalent metal ion is obtained by ionic crosslinking of a polymer of an acidic group-containing polymerizable monomer to a cured product component in a prosthesis or resin cement that is a cured resin. Synergistic effect between polymer curing and polymerization, in particular, the affinity between the resin cement and the prosthesis is enhanced by the action of the ionic crosslinked product, and the permeability of the range cement into the resin cured product (prosthesis) is increased. Thus, a high adhesive strength can be ensured.

  This polyvalent metal ion is a divalent or higher valent metal ion that can be bonded to the acidic group of the polymerizable monomer (A1), and any ion can be used as long as it can bond to the acidic group. Multivalent ions may be used, but from the viewpoint of being used for dentistry, calcium, strontium, barium, aluminum, scandium, ytterbium, titanium, zinc, magnesium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel Ions such as copper and lanthanoid are preferred. Among these, trivalent or higher ions are suitable because of their high adhesiveness, and they contain aluminum ions, lanthanum ions, and titanium ions as components. From the viewpoint of the above, it is most preferable.

  In the primer composition of the present invention, the polyvalent metal ion (B) as described above is present in an amount of 1.0 to 12.0 meq per 1 g of the monomer component (A) described above. preferable. In order to ensure the storage stability of the developed primer in one liquid (one package), it is present in an amount of 1.0 to 7.0 meq per 1 g of the monomer component (A) described above. It is more preferred that it is present in an amount of 1.5 to 6.8 meq. The presence of polyvalent metal ions in such an amount makes it possible to form a strong adhesive layer at the interface between the cured resin (prosthesis) and the resin cement by appropriate ionic crosslinking, The permeability of the resin cement to the cured resin is increased. When the amount of polyvalent metal ions is less than the above range, ionic crosslinking is insufficient, and the adhesive strength may be insufficient. Further, when the amount is larger than the above range, not only the permeability by the acidic group-containing polymerizable monomer (A1) is lowered, but also the volatilization necessary for ensuring the storage stability in one liquid (one package). The amount of the organic solvent (C) becomes large, and the primer composition tends to be insufficient after the primer composition is applied to the surface of the prosthesis, which is a range-cured product, and air blown. In this case, the adhesive strength is reduced.

  In the present invention, as the ion source for allowing the polyvalent metal ion (B) to be present in the amount as described above, the polyvalent metal alkoxide, water-soluble salt, water-soluble hydroxide, water-soluble oxide described above are used. An ionic compound such as a complex salt can be used in an amount corresponding to its solubility or dissociation degree, but a polyvalent metal ion-eluting filler (hereinafter simply referred to as a polyvalent metal filler) can also be used. . That is, since the polyvalent metal filler has a function as a filler for improving the mechanical strength of the adhesive layer, it ensures higher adhesive strength between the resin-cured prosthesis and the resin cement. Because you can.

  Examples of the polyvalent metal alkoxide as a polyvalent metal ion source include aluminum triisopropoxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, lanthanum triisopropoxide, scandium triisopropoxide, ytterbium triiso Examples include propoxide, chromium triisopropoxide, titanium tetraisopropoxide, zirconium tetraisopropoxide, iron (III) ethoxide, copper (II) ethoxide, zinc bis (2-methoxyethoxide) and the like. Examples of water-soluble salts of polyvalent metals include aluminum salicylate and aluminum chloride. Examples of water-soluble hydroxides of polyvalent metals include aluminum hydroxide, calcium hydroxide, lanthanum hydroxide, water Examples thereof include magnesium oxide and barium hydroxide. Further, examples of water-soluble oxides include aluminum oxide, and complex salts include vanadium (III) tetrakisacetylacetonate, manganese (III) tetrakisacetylacetonate, cobalt (III) tetrakisacetylacetonate, nickel (II ) Tetrakis acetylacetonate and the like can be exemplified.

  Further, the above polyvalent metal filler is particularly preferably used in the present invention, and this filler is monovalent such as sodium as long as the above polyvalent metal ion can be eluted within the above range. However, if too much monovalent metal ions are included, the crosslinkability of polyvalent metal ions will be affected, so monovalent metal ions should be contained as much as possible. It is preferable that the content of monovalent metal ions contained in the polyvalent metal filler is 10 mol% or less, particularly 5 mol% or less of the polyvalent metal ion content.

  In the present invention, the amount of polyvalent metal ions present in the primer composition is determined by measuring the concentration of various ions by ICP emission spectroscopic analysis or atomic absorption analysis, etc. The amount of ionic bonds with the body component (A) is expressed in terms of milliequivalents per gram of the monomer component (A), and each polyvalent metal ion concentration per gram of the monomer component (A) It can be determined as the sum of values obtained by multiplying (mmol / g) by the valence of each metal ion.

  Moreover, the elution of the polyvalent metal ions from the polyvalent metal filler is usually eluted in about 3 to 12 hours at room temperature (23 ° C.) after preparing the primer composition. Therefore, the amount of polyvalent metal ions when using a polyvalent metal filler is substantially equal to the amount of polyvalent metal ions after 24 hours of preparation at room temperature (23 ° C.), and the total amount contained in the polyvalent metal filler. It can be calculated from the amount of polyvalent metal ions and the content of the monomer component (A) in the primer composition.

  The polyvalent metal filler described above is not particularly limited as long as it can elute polyvalent metal ions in the above-mentioned range. However, the polyvalent metal ion is a counter anion that can be eluted simultaneously with the polyvalent metal ions. When it is contained as a salt, the eluted and dissociated counter anion may adversely affect the adhesive strength (this is the same as when a water-soluble salt of a polyvalent metal is used). Therefore, in the present invention, it is preferable to use a polyvalent metal filler that does not elute the counter anion of the polyvalent metal ion at the same time. Examples of the polyvalent metal filler that satisfies such conditions include glass having a chain, layered, or network-like skeleton, and containing a polyvalent metal ion in the gap between the skeletons.

  As the above glasses, those containing oxide glass components such as aluminosilicate glass, borosilicate glass and soda lime glass, and those containing fluoride glass components such as zirconium fluoride glass are suitable. . That is, the polyvalent metal filler made of glass containing these components becomes porous particles having a network-like structure after the polyvalent metal ions are eluted, and the cured product strength (adhesion layer) of the primer composition Strength).

  In the present invention, a polyvalent metal filler made of aluminosilicate glass is more preferably used particularly in terms of improving the strength of the cured body, and further, so-called fluoride ions that reinforce the tooth substance are gradually released after bonding. A polyvalent metal filler made of fluoroaluminosilicate glass having a sustained release of fluorine is most preferably used.

  The elution characteristics of polyvalent metal ions in the polyvalent metal filler can be controlled by the mixing ratio of various elements contained in the filler. For example, if the content of polyvalent metal ions such as aluminum and calcium is increased, these elution amounts generally increase, and the elution amount of polyvalent metal ions can be changed by changing the content of sodium and phosphorus. Therefore, the elution characteristics of polyvalent metal ions can be controlled relatively easily.

  The elution characteristics of the polyvalent metal filler can also be controlled by using a generally known method. As a typical method, the polyvalent metal filler is treated with an acid to form a polyvalent metal on the filler surface. A method of previously removing ions and controlling the elution characteristics is known. As the acid used in this method, generally known acids such as inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as maleic acid and citric acid are used. The acid concentration, treatment time, etc. may be appropriately determined according to the amount of ions to be removed.

Moreover, the said fluoro aluminosilicate glass suitable as a polyvalent metal filler in this invention can use the well-known thing used for the glass ionomer cement used for dentistry, for example. Generally known fluoroaluminosilicate glass is expressed in terms of ion mass% and has the following composition.
Silicon; 10 to 33%, especially 15 to 25%
Aluminum; 4-30%, especially 7-20%
Alkaline earth metals; 5-36%, especially 8-28%
Alkali metal; 0-10%, especially 0-10%
Phosphorus; 0.2-16%, especially 0.5-8%
Fluorine; 2-40%, especially 4-40%
Oxygen; remaining amount

  Moreover, what substituted a part or all of calcium in said alkaline-earth metal with magnesium, strontium, and barium is also suitable. Further, sodium is most commonly used as the alkali metal, but it is also preferable to replace part or all of the alkali metal with lithium, potassium, or the like. Furthermore, if necessary, glass in which a part of the aluminum is replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like can be used as the polyvalent metal filler.

  The particle shape of the polyvalent metal filler described above is not particularly limited, and may be pulverized particles or spherical particles obtained by normal pulverization, and may be mixed with plate-like, fiber-like particles as necessary. .

In addition, from the viewpoint that the polyvalent metal filler can be uniformly dispersed in the primer composition, for example, an average particle diameter (D ₅₀ ) in terms of volume measured by a laser diffraction scattering method is 0.01 μm to ₅ μm, In particular, it should be in the range of 0.05 μm to 3 μm, most preferably 0.1 μm to 2 μm. Furthermore, from the viewpoint that the amount of elution of polyvalent metal ions can be easily adjusted to the above-mentioned range, 0.1 g of the filler was eluted when immersed in 10 ml of 10% by weight maleic acid aqueous solution at a temperature of 23 ° C. for 24 hours. The amount of polyvalent metal ions is preferably 5.0 to 500 meq / g-filler, particularly 10 to 100 meq / g-filler. The amount of polyvalent metal ions at this time can also be measured by ICP emission spectroscopic analysis or atomic absorption analysis. The amount of polyvalent metal ions eluted after 24 hours under the above conditions is hereinafter also referred to as “24 hours eluted ion amount”.

<Volatile organic solvent (C)>
In the present invention, the volatile organic solvent (C) is used for uniformly dispersing various components. Such an organic solvent (C) is preferably blended in the range of 30 to 150 parts by mass per 100 parts by mass of the monomer component (A) described above. That is, if the blending amount of the organic solvent (C) is less than 30 parts by mass, the uniformity of the primer composition may not be sufficient, and the permeability to the cured resin product (prosthesis) is also reduced. Can not get a good adhesion. On the other hand, if the blending amount exceeds 150 parts by mass, it becomes difficult to remove the organic solvent after applying the primer composition to the adhesive surface of the prosthesis, and excessive air blowing is required to remove the organic solvent. As a result, even the adhesive component is removed by excessive air blowing, and the adhesive strength may be lowered due to a decrease in the concentration of the adhesive component.
Furthermore, the volatile organic solvent (C) has a function of preventing gelation derived from the above-described polyvalent metal ions, and thereby, rapid gelation when the polyvalent metal ions are blended. Therefore, the primer composition can be easily coated on a predetermined part of the prosthesis, and the restoration of the prosthesis can be performed smoothly. Therefore, the use of such an organic solvent (C) is effective in improving the storage stability of the primer composition. For example, the organic solvent (C) allows polyvalent metal ions to have a specific concentration. By diluting, the primer composition can be stored in a one-packed state in which all the components are blended (that is, in the form of one package).

The organic solvent (C) at the time of storing in one liquid state is in the range of 30 to 150 parts by mass per 100 parts by mass of the monomer component (A) described above, and the following formula (I):
α ≧ 20 · X (I)
In the formula, α is the polymerizable monomer component (A) of the water-soluble organic solvent (C).
It is a blending amount per 100 parts by mass,
X is per 1 g of the polymerizable monomer component (A) of the polyvalent metal ion.
Is a number indicating the amount (meq) of
It is preferable that it is blended in such an amount that satisfies the condition represented by
Further, even when the blending amount of the water-soluble organic solvent (C) is in the range of 30 to 150 parts by mass, when the condition of the formula (I) is not satisfied (that is, α <20 · X In this case, the degree of dilution of the polyvalent metal ions is low, so that gelation is likely to occur, and the storage stability in the form of one package in which all components are blended is reduced. It is necessary to store the monomer component (A) and the polyvalent metal ion (B) in separate packages.

In the present invention, from the viewpoint of obtaining particularly high adhesive strength, the blending amount of the organic solvent (C) is preferably in the range of 60 to 100 parts by mass, and further increases the storage stability. From this, this compounding quantity is the following formula (II):
α ≧ 25 · X (II)
In the formula, α and X are as shown in formula (I):
It is good to be satisfied.

  After applying the primer composition of the present invention to the surface of the prosthesis made of a resin cured product (the surface to which the resin cement is to be bonded), the organic solvent (C) is volatilized by air blowing so that the active ingredient is present on the surface of the prosthesis. Concentrated, the ionic crosslinking between the acidic group-containing polymerizable monomer and the polyvalent metal ions is promoted, and the adhesion of the resin-cured prosthesis surface to the resin cement is enhanced. Therefore, the organic solvent (C) used in the present invention needs to be volatile at room temperature.

  In this specification, “volatile” means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. “Water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 ml or more.

  In the present invention, the organic solvent (C) is preferably water-soluble from the viewpoints of dilutability with respect to the polyvalent metal ion (B) and compatibility with water (D) described below.

  Examples of the volatile organic solvent (C) preferably used in the present invention include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone and the like. A plurality of these organic solvents can be mixed and used as necessary. In view of toxicity to the living body, ethanol, isopropyl alcohol and acetone are preferable.

<Water (D)>
In the present invention, the water of the component (D) has a function as a solvent for uniformly dispersing various components, and at the same time, the acidic group-containing polymerizable monomer (A1) and the polyvalent metal ion (B). It is necessary for the promotion of ion binding. As this water, distilled water or deionized water which does not substantially contain impurities harmful to storage stability and medical components is preferably used.

  The amount of such component (D) added to water is 3 to 30 parts by mass, particularly 5 to 25 parts by mass, per 100 parts by mass of the monomer component (A). If the amount of water added is less than this range, ionic crosslinking will be insufficient and high adhesive strength cannot be obtained. Further, if it is used in a larger amount than the above range, it becomes difficult to completely remove water after applying this primer composition to the prosthesis surface, and sufficient adhesive force cannot be obtained due to the remaining water.

<Inorganic filler (E)>
To the primer composition of the present invention, an inorganic filler (E) can be added in order to increase the strength of the adhesive layer existing between the resin cement and the prosthesis after the resin cement is cured. . This inorganic filler (E) is distinguished from the polyvalent metal filler described above in that it does not elute polyvalent metal ions, and silica, silica / zirconia, silica / titania, silica / alumina, etc. Those composed of the composite inorganic oxide are preferably used.

  The particle size of such an inorganic filler (E) is not particularly limited, but the primary particle size is preferably 5 μm or less, more preferably 0.001 to 1 μm, and most preferably 0.01 to 0.5 μm. Further, the particle shape is not limited at all, and may be either an indefinite shape or a spherical shape.

  These inorganic fillers (E) improve the compatibility with the polymerizable monomer component (A) by hydrophobizing with a surface treatment agent typified by a silane coupling agent, thereby improving mechanical strength and water resistance. Further improvement can be achieved.

  Silane coupling agents used for such hydrophobization include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltrichlorosilane. , Vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropyl Methyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Tokishishiran, N- phenyl--γ- aminopropyltrimethoxysilane, etc. hexamethyldisilazane is preferably used.

  The addition amount of these inorganic fillers (E) is usually in the range of 2 to 20 parts by mass, particularly in the range of 5 to 10 parts by mass per 100 parts by mass of the monomer component (A). If the amount is less than this range, the effect of improving the strength is not sufficiently obtained. The effect of improving the strength cannot be obtained sufficiently.

<Photopolymerization initiator (F)>
In the primer composition of the present invention, a photopolymerization initiator (F) can be blended with the composition in order to further improve the adhesion to the resin cement. As such a photopolymerization initiator (F), a compound that itself generates radical species by light irradiation or a mixture obtained by adding a polymerization accelerator to such a compound is used.

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

  Further, tertiary amines and the like are used as the polymerization accelerator. Specific examples thereof are as follows.

Tertiary amines;
N, N-dimethylaniline,
N, N-diethylaniline,
N, N-di-n-butylaniline,
N, N-dibenzylaniline,
N, N-dimethyl-p-toluidine,
N, N-diethyl-p-toluidine,
N, N-dimethyl-m-toluidine,
p-bromo-N, N-dimethylaniline,
m-chloro-N, N-dimethylaniline,
p-dimethylaminobenzaldehyde,
p-dimethylaminoacetophenone,
p-dimethylaminobenzoic acid,
p-dimethylaminobenzoic acid ethyl ester,
p-dimethylaminobenzoic acid amyl ester,
N, N-dimethylanthranic acid methyl ester,
N, N-dihydroxyethylaniline,
N, N-dihydroxyethyl-p-toluidine,
p-dimethylaminophenethyl alcohol,
p-dimethylaminostilbene,
N, N-dimethyl-3,5-xylidine,
4-dimethylaminopyridine,
N, N-dimethyl-α-naphthylamine,
N, N-dimethyl-β-naphthylamine,
Tributylamine,
Tripropylamine,
Triethylamine,
N-methyldiethanolamine,
N-ethyldiethanolamine,
N, N-dimethylhexylamine,
N, N-dimethyldodecylamine,
N, N-dimethylstearylamine,
N, N-dimethylaminoethyl acrylate,
N, N-dimethylaminoethyl methacrylate,
2,2 ′-(n-butylimino) diethanol and the like.

  The blending amount of such a photopolymerization initiator (F) is not particularly limited as long as it is an effective amount capable of curing the primer composition, and may be set as appropriate. A) It is good to set it as the range of 0.01-10 mass parts per 100 mass parts, especially 0.1-5 mass parts. If it is less than 0.01 part by mass, the polymerization tends to be insufficient, and if it exceeds 10 parts by mass, the strength of the produced polymer is undesirably lowered. The polymerization curing accelerator described above may be used in the photopolymerization initiator (F) in a catalyst amount of about several percent. Therefore, even if an amine compound is used as a polymerization accelerator, the amount is extremely small and does not cause a bad smell or coloring problem.

<Other ingredients>
To the primer composition of the present invention, an organic thickener such as a polymer compound such as polyvinyl pyrrolidone, carboxymethyl cellulose, and polyvinyl alcohol can be added as long as the performance is not deteriorated. Various additives such as ultraviolet absorbers, dyes, antistatic agents, pigments, and fragrances can be selected and used as necessary.

  In addition, when the primer composition of the present invention is applied to the surface of a prosthesis, the coated surface is covered with resin cement, so that it is hardly affected by oxygen in the air at the time of curing, and oxygen in the air is bonded. Although it does not affect the force, a tertiary amine shown as an example of a polymerization curing accelerator can be added in order to minimize curing inhibition due to oxygen dissolved in the composition.

<Application of primer composition>
The primer composition of the present invention has, for example, a polyvalent metal ion (B), a volatile organic solvent (C), and water (D) that are adjusted within the predetermined range described above. Since gelation by metal ions is effectively suppressed and storage stability is excellent, each component is mixed at once and stored in a sealed container in the form of one liquid, that is, in the form of a single package. A predetermined amount is taken out and applied to a predetermined site. That is, in use, the troublesome operation of mixing each component is not necessary, and the labor of a dentist or the like can be reduced, and stable and constant adhesive strength can be secured. In addition, since storage stability is impaired when the compounding ratio of each component is outside the predetermined range, for example, the acidic group-containing polymerizable monomer component (A1) and the polyvalent metal ion component (B) Are stored in separate packages, and the other ingredients are stored in either the package containing (A1) or (B), or mixed in both packages in an appropriate volume ratio. It will be mixed.

  Such a primer composition of the present invention is used for improving adhesiveness by surface treatment of a resin-cured prosthesis, for example, when fixing the prosthesis to a tooth restoration site or at a tooth restoration site. It is used for repair when a fixed prosthesis is damaged.

  When fixing the prosthesis to the tooth restoration site, the surface of the prosthesis molded into a predetermined shape is appropriately polished, and then a predetermined amount of the primer composition is applied, and the volatility in the composition by air blow After removing the organic solvent (C) and water (D), the resin cement paste is overcoated on the coated surface, this is adhered to the restoration site of the tooth, and the resin cement paste is cured by chemical polymerization, photopolymerization, etc. Thus, the prosthesis is adhesively fixed to the restoration site of the tooth by the resin cement.

  In addition, when used for repairing a damaged prosthesis itself, for example, for each of the prosthesis and the prosthesis remaining on the teeth, the primer composition of a predetermined amount is applied to the fractured surface, After removing the organic solvent, etc. by air blowing, as described above, it is possible to re-fix the prosthesis that has been broken and dropped by overcoating the resin cement paste on the application surface of any of the prosthesis and allowing it to harden. it can. Further, instead of the broken prosthesis, a prosthesis newly formed in the same shape as this can be used, and the same can be adhered and fixed to the prosthesis remaining on the tooth.

  In addition, the process until the primer composition is applied to the prosthesis, and further the resin cement paste is applied, so that the volatile organic solvent (C) is not volatilized from the primer composition taken out from the container. It should be done as quickly as possible, for example in a few minutes. This is because if the amount of the volatile organic solvent (C) is volatilized and the amount decreases, an improvement in adhesion cannot be expected.

<Hardened resin prosthesis>
In the present invention, the cured resin prosthesis treated with the primer composition described above is not particularly limited as long as it is formed by curing the resin component, and is a known dental curable composition per se. It may be obtained by curing. For example, such a curable composition generally contains a radical polymerizable monomer and an inorganic filler as main components.

  As the radical polymerizable monomer, a (meth) acrylate-based monomer is generally used, and in particular, a polyfunctional polymerizable monomer (A2) having no acidic group described with respect to the primer composition of the present invention. ) Is mainly used. As the inorganic filler, metal oxides such as silica and alumina, composite oxides such as silica-titania and silica-zirconia, barium glass and the like are mainly used. The inorganic filler is blended in the curable composition in an amount of about 50 to 95% by mass on the basis of two components with the radical polymerizable monomer. The curable composition usually contains a photopolymerization initiator, a chemical polymerization initiator or a thermal polymerization initiator in an amount effective for curing. Such curable compositions are disclosed in, for example, JP-A No. 2002-255721, JP-A No. 2001-139411, JP-A No. 2003-95836, JP-A No. 2000-80013, and JP-A No. 10-218721. It is described in Kaihei 11-100305, JP-A-7-196431, JP-A-6-107516, re-publication 2002-005752, and the like.

  The curable composition as described above is formed into a predetermined shape corresponding to a restoration site of a tooth by a dental technician, and cured by light irradiation, heating, etc., so that an abutment tooth, a resin inlay, a resin crown, etc. Although applied to dental restoration as a dental prosthesis, the primer composition of the present invention exhibits excellent adhesion to the prosthesis, even though the prosthesis is a cured product. That is, the conventionally known primer applied to such a resin-cured prosthesis is low in adhesion to the prosthesis because the prosthesis is a cured product and has few active points. The composition itself contains components that exhibit excellent adhesion to the prosthesis, as well as exhibit high permeability to the prosthesis, and are bonded by curing and ionic crosslinking. Therefore, high adhesiveness is shown with respect to the prosthesis which is a resin cured material.

<Resin cement>
Resin cement used for adhering and fixing a prosthesis to a dental restoration site is known as a dental adhesive. For example, JP-A-5-170618, JP-A-6-16520, and JP-A-8-319209 are known. No. 9, JP-A-9-3109, JP-A-2002-161013, JP-A-2003-96122, etc., which are cured by light irradiation, heating, etc. By this, it is used for adhesion | attachment of a prosthesis and tooth quality or prosthesis.

  That is, as described in the above publications and the like, this resin cement includes a (meth) acrylate polymerizable monomer as a polymerizable monomer, and further includes a photopolymerization initiator, a chemical polymerization initiator, and the like. A polymerization initiator and an inorganic filler are blended.

  For example, in such a resin cement, the (meth) acrylate-based polymerizable monomer does not have the acidic group-containing polymerizable monomer (A1) or acidic group described as a blending component in the primer composition of the present invention. Of polyfunctional or monofunctional polymerizable monomers, those having a (meth) acrylate group are generally used.

  As the photopolymerization initiator, those exemplified as the photopolymerization initiator (F) in the above-described primer composition of the present invention are generally used, and among them, α-diketone / tertiary amine polymerization initiation is particularly used. Agent, dye such as coumarin, photoacid generator such as trichloromethyl group-substituted s-triazine, and dye / photoacid generator / arylborate compound photopolymerization initiator comprising arylborate compound such as tetraphenylborate / amine salt Are preferably used. Further, as the chemical polymerization initiator, a peroxide / amine polymerization initiator comprising a peroxide such as benzoyl peroxide and a tertiary amine such as N, N-diethanol-p-toluidine; acidic compound / Polymerization initiator comprising an aryl borate compound; Polymerization initiator comprising an acidic compound / aryl borate compound / metal complex; Polymerization initiator comprising an acidic compound / aryl borate compound / metal complex / organic peroxide; Partial oxide of tributylborane Alkyl metal compounds such as: barbituric acid based initiators such as n-butyl barbituric acid / copper chloride are commonly used. Such a polymerization initiator is blended in a so-called catalytic amount in the resin cement.

  Furthermore, an inorganic filler is mix | blended in order to improve the mechanical strength of hardened | cured material, and generally the inorganic filler is mix | blended in the quantity of 25-75 mass% in resin cement. As such an inorganic filler, the thing similar to what is mix | blended in the curable composition for forming the resin cured material prosthesis mentioned above is used.

  The above-mentioned resin cement is applied to the surface of a cured resin prosthesis coated with the above-described primer composition, and is cured by light irradiation or heating. This cured product is a polymerization compounded in the primer composition. Since it is copolymerized with the functional monomer component (A) and bonded to the cured product (adhesive layer) of the primer composition by ionic crosslinking, it is firmly bonded and fixed to the prosthesis through the cured product.

<Primer kit>
As described above, in the primer composition of the present invention in which the usage amount of each component is adjusted to a predetermined ratio, this is accommodated in a predetermined sealed container, and in the form of a single package, the resin cured product prosthesis Although it is used as a primer, it contains an acidic group-containing polymerizable monomer, and thus exhibits a certain degree of adhesion to other prosthetics (the monomer is bonded to metal atoms and hydrogen in the prosthetics). Because it forms a bond). Therefore, by adding an effective adhesive component to other prostheses, as a primer for other prosthesis, for example, a base metal alloy prosthesis, a noble metal alloy prosthesis, or a ceramic prosthesis Can also be used.

  For example, as a primer for a noble metal alloy prosthesis, it is known that a sulfur atom-containing polymerizable monomer is an effective adhesive component as a polymerizable monomer. That is, since the sulfur atom in this monomer forms a chemical bond with the noble metal atom, the primer containing such a sulfur atom-containing polymerizable monomer is effective as a primer for a noble metal alloy prosthesis. That is why. Therefore, by adding a predetermined amount of a sulfur atom-containing polymerizable monomer to the primer composition of the present invention, the primer composition of the present invention can be diverted to a primer for a noble metal alloy prosthesis.

  Examples of the sulfur atom-containing polymerizable monomer as described above include those disclosed in JP-A No. 2000-248201, specifically, tautomers represented by the following general formulas (a1) to (a5). A radically polymerizable compound capable of forming a mercapto group (SH) depending on the properties, a radically polymerizable disulfide compound represented by the following general formulas (a6) to (a9), and a general formula (a10) to (a11) Radical polymerizable thioether compounds are known.

In the above formulas (a1) to (a11),
R ¹ is a hydrogen atom or a methyl group,
R ² is an alkylene group having 1 to 12 carbon atoms, a —CH ₂ —C ₆ H ₄ —CH ₂ group,
_{- (CH 2) p-Si} (CH 3) 2 - (CH 2) q- group (Here, p and q are 1
An integer of ~ 5),
Z ¹ is an —O—CO— group, an —OCH ₂ — group or an —OCH ₂ —C ₆ H ₄ — group,
Z ² is an —O—CO— group, a —C ₆ H ₄ — group or a bond (the group R 2 and unsaturated carbon are directly bonded);
Y is —S—, —O— or —N (R ′) — (wherein R ′ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

Among these, a radically polymerizable compound capable of forming a mercapto group (SH) by tautomerism represented by the general formulas (a1) to (a5) is preferable from the viewpoint of adhesiveness.
Silane coupling agents are also known as effective adhesive components for ceramic prostheses. Therefore, what added the silane coupling agent to the primer composition of this invention can be used suitably not only as a primer for resin prosthesis products but also as a primer for ceramic prostheses.

  In addition, as a silane coupling agent as mentioned above, the silane compound illustrated as a surface treating agent of the inorganic filler (E) mentioned above is used, for example.

  As understood from the above description, the primer composition of the present invention is a resin-cured prosthesis primer that is contained in a predetermined sealed container, separately from other prosthesis. In contrast, an effective sulfur atom-containing polymerizable monomer (hereinafter simply referred to as a sulfur monomer) and a composition obtained by dissolving or dispersing an adhesion improving component such as a silane coupling agent in a volatile organic solvent These can be accommodated in other sealed containers as primer aids for expanding compatibility and used as kits for dental prostheses. That is, in such a kit, the primer composition of the present invention is used as a primer for a cured resin prosthesis and a base metal alloy prosthesis. The quantitative amount may be added to and mixed with the primer composition of the present invention under an inert light such as red light. Therefore, such a kit is not limited to a resin-made prosthesis, but may be any other optional component. It can be used as a primer for the prosthesis.

  In the primer aid for expanding compatibility, the adhesion improver component (sulfur monomer and / or silane coupling agent) is uniformly dissolved or dispersed as the volatile organic solvent, and the present invention. Although it will not be restrict | limited especially if it can mix uniformly with the primer composition of this, Generally, the same solvent as the volatile organic solvent (C) mix | blended with the primer composition of this invention is used. Is preferred. In addition, an additive such as a polymerization inhibitor may be blended in the primer aid for expanding compatibility.

  The adhesion improver component in the primer aid for expanding compatibility is preferably set to a concentration of, for example, 0.1 to 20% by mass, particularly 0.5 to 15% by mass. That is, if this concentration is too low, the amount of the volatile organic solvent becomes excessive when added to the primer composition of the present invention, and it takes a long time to remove the volatile organic solvent by air blow or the like. May decrease. Moreover, if the concentration of the adhesion improving component is higher than necessary, it may be difficult to uniformly disperse the adhesion improving component when added to the primer composition of the present invention.

  Further, the adhesion improver component uses both a sulfur monomer and a silane coupling agent, and these may be dissolved or dispersed in a volatile organic solvent, or the sulfur monomer or silane cup. Only one of the ring agents can be transferred. When either one is used, for example, a mixture of a sulfur monomer in an organic solvent is used as a primer aid for a precious metal prosthesis, and a mixture of a silane coupling agent in an organic solvent is made of a ceramic. It may be used as a primer aid for prosthetics. Specifically, the above-described book containing a package containing a compatibility enhancing primer aid containing a sulfur-based monomer and a package containing a compatibility enhancement primer aid containing a silane coupling agent. The primer composition of the invention can be used in combination as a package containing the primer composition for use as a primer kit.

  When the primer kit described above is used as a primer for other prosthesis (a primer for a non-metal alloy or noble metal alloy prosthesis) using the improvement in adhesion by a sulfur-based monomer, the primer composition of the present invention It is preferable to mix so that the concentration of the sulfur monomer when mixed with the product is 0.01 to 10% by mass based on the total polymerizable monomer. When used as a primer for another prosthesis (for example, a primer for a ceramic prosthesis), the concentration of the silane coupling agent when mixed with the primer composition of the present invention is 0 per total polymerizable monomer. It is preferable to mix so that it may become a density | concentration of 1 thru | or 15 mass%.

The present invention will be specifically described below with reference to experimental examples, but the present invention is not limited to these experimental examples.
Various components used in each experimental example and the abbreviations, abbreviations, adhesion strength measuring method, storage stability evaluation method, and polyvalent metal ion content measuring method shown in each experimental example are as follows.

<Polymerizable monomer component (A)>
[Acid group-containing polymerizable monomer (A1)]
PM:
2: 1 mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate MDP:
10-methacryloyloxydecyl dihydrogen phosphate MAC-10:
11-methacryloyloxy-1,1-undecanedicarboxylic acid 4-META:
4-Methacryloyloxyethyl trimellitic acid

[Polymerizable monomer containing no acidic group (A2)]
D26E:
2,2'-bis (4- (methacryloxyethoxy) phenyl) propane BisGMA:
2,2'-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane 3G:
Triethylene glycol dimethacrylate HEMA:
2-hydroxyethyl methacrylate MMA:
Methyl methacrylate AAEM:
2-Methacryloxyethyl acetyl acetate

<Metal ion (B) supply source>
[Polyvalent metal filler]
MF1:
Multivalent metal filler obtained in Production Example 1 (average particle size: 0.5 μm, 24 hours elution ion amount: 10 meq / g filler)
MF2:
Multivalent metal filler obtained in Production Example 2 (average particle size: 0.5 μm, 24 hour elution ion amount: 25 meq / g filler)
MF3:
Polyvalent metal filler obtained in Production Example 3 (average particle size: 0.5 μm, 24 hour elution ion amount: 50 meq / g filler)

[Alkoxides of polyvalent metals, etc.]
Aluminum triisopropoxide: Al (O-iPr) ₃
Aluminum hydroxide: Al (OH) ₃
Lanthanum triisopropoxide: La (Oi-Pr) ₃
Lanthanum hydroxide: La (OH) ₃
Scandium triisopropoxide: Sc (Oi-Pr) ₃
Ytterbium triisopropoxide: Yb (Oi-Pr) ₃
Chromium (III) triisopropoxide: Cr (Oi-Pr) ₃
Manganese (III) tetrakisacetylacetonate: Mn (acac) ₃
Iron (III) ethoxide: Fe (OEt) ₃
Cobalt (III) tetrakisacetylacetonate: Co (acac) ₃
Magnesium hydroxide: Mg (OH) ₂
Calcium hydroxide: Ca (OH) ₂
Barium hydroxide: Ba (OH) ₂
Nickel (II) tetrakisacetylacetonate: Ni (acac) ₂
Copper (II) ethoxide: Cu (OEt) ₂
Zinc bis (2-methoxyethoxide): Zn (OCH ₂ CH ₂ OMe) ₂
Titanium tetraisopropoxide: Ti (Oi-Pr) ₄
Zirconium tetraisopropoxide Zr (Oi-Pr) ₄

<Volatile organic solvent (C)>
Ethyl alcohol: Et-OH
Isopropyl alcohol: IPA
acetone

<Inorganic filler filler (E)>
F1:
Spherical silica-titania (γ-methacryloyloxypropyltrimethoxysilane hydrophobized product) having a particle size of 0.08 μm
F2:
Amorphous silica with a particle size of 0.02 μm (treated with methyltrichlorosilane)

<Polymerization initiator (F)>
CQ: camphorquinone DMBE: ethyl p-N, N-dimethylaminobenzoate TPO:
2,4,6-trimethylbenzoyldiphenylphosphine oxide

<Polymerization inhibitor>
BHT: 2,6-di-t-butyl-p-cresol

<Other ingredients>
[Sulfur monomer]
MTU-6: 6-methacryloyloxyhexyl-2-thiouracil-5
-Carboxylate [silane coupling agent]
MPS: 3-methacryloyloxypropyltrimethoxysilane

<Adhesiveness to resin-made prosthesis>
A “Pearl Esthe” made by Tokuyama Dental Co., Ltd. is prepared as a commercially available dental resin. This dental resin is filled in a 10 × 10 × 3 mm Teflon mold, and a transparent polypropylene film is pressed against light to block light. Polymerization and heat polymerization (100 ° C. × 15 minutes) were continuously performed to prepare a cured resin.
The surface of the cured resin (10 × 10 × 3 mm) was smoothed by polishing with # 800 water-resistant abrasive paper, and then an adhesive tape with 3 mmφ holes was attached to the polished surface. That is, the hole portion of the adhesive tape becomes a simulated cavity and becomes a bonding surface.

  Next, the primer composition prepared in each of the examples and comparative examples was applied to the hole portion serving as a simulated cavity with a sponge, allowed to stand for 20 seconds, and then compressed air was sprayed for about 5 seconds. After that, “Bistite II” manufactured by Tokuyama Dental Co., Ltd. as a dental resin cement was filled in the hole (simulated cavity) where the primer composition was applied, and a stainless steel attachment with a diameter of 8 mm was pressed from above to test the adhesion. A piece was made.

  Next, after the above-mentioned adhesive test piece is immersed in 37 ° C. water for 24 hours, the above-mentioned resin cured body and adhesion test are conducted at a crosshead speed of 2 mm / min using a tensile tester (manufactured by Shimadzu Corporation). The adhesive strength with the piece (stainless steel attachment) was measured. In addition, the tensile bond strength was measured by the said method about four test pieces per test, and the average value was evaluated as adhesive strength.

<Adhesiveness to dental alloy prosthesis>
Tokuyama Dental Dental Cobalt-Chromium Alloy “Wachrome” (10 × 10 × 3 mm) as the base metal alloy adherend, and Tokuyama Dental Dental Gold-Silver-Palladium Alloy “Gold” as the precious metal alloy adherend Para 12 ”(10 × 10 × 3 mm) was prepared.
Each surface of the adherend is polished with # 1500 water-resistant abrasive paper and then sandblasted, and the treated surface has a hole that becomes a simulated cavity in exactly the same manner as the adhesiveness to the resin-cured prosthesis. An adhesive test piece was prepared by applying a pressure sensitive adhesive tape with a primer composition prepared in each of the examples and comparative examples, spraying with compressed air, filling a resin cement, and a stainless steel attachment. In the same manner, the adhesive strength between the base metal alloy adherend or the noble metal alloy adherend and the adhesion test piece (stainless steel attachment) was measured.

<Adhesiveness to ceramic prosthesis>
As a ceramic adherend, dental ceramic “Ceraeste” (10 × 10 × 3 mm) made by Tokuyama Dental was prepared.
The surface of the ceramic adherend is exactly the same as the adhesiveness to the resin-cured prosthesis, polished with water-resistant abrasive paper, and adhesive tape attached to the polished surface. The prepared primer composition was filled, compressed air was sprayed, resin cement was filled, and an adhesion test piece was prepared by pressure contact with a stainless steel attachment. The adhesion strength with an adhesion test piece (stainless steel attachment) was measured.

<Measurement of polyvalent metal ion content>
The sample primer composition was stirred for 24 hours immediately after preparation, after which the sample primer composition was weighed into a 100 ml sample tube and diluted to 1% by volume with IPA.
This diluted solution was filtered with a syringe filter, and the concentration of polyvalent metal ions (mmol / g) per 1 g of the polymerizable monomer component (A) was measured using ICP (inductively coupled plasma) emission spectrometry. . In addition, when there are a plurality of polyvalent metal ions, by calculating the sum of values obtained by multiplying each obtained ion concentration by the respective ion valence, the amount of ionic crosslinking with respect to 1 g of component (A), that is, The amount of polyvalent metal ions (meq) was determined.

<Evaluation of storage stability>
After preparing the primer composition and storing it in an incubator at 37 ° C. for one month, using this composition, the adhesive strength to the resin cured product is measured using the same method as the above-described adhesive strength measuring method, The storage stability was evaluated by comparing with the adhesive strength (initial adhesive strength) of the composition before storage at 37 ° C.

<Example 1>
Formula 1 below (Primer A):
Acidic group-containing polymerizable monomer (A1): 2.5 g of PM
Polymerizable monomer (A2): 3.0 g of BisGMA, 2.0 g of 3G, 2.5 g of HEMA
Volatile organic solvent (C): 3.0 g of isopropanol (IPA)
Other components: 0.003 g of BHT (polymerization inhibitor)
Formula 2 below (Primer B):
Multivalent metal ion (B) source: 1.2 g aluminum triisopropoxide Volatile organic solvent (C): 7.0 g isopropanol (IPA)
Water (D): In accordance with 2.0 g of distilled water, each of the above components was stirred and mixed to prepare a two-component primer composition. Immediately before use, the two liquids are collected in equal masses and mixed to make a uniform solution. About this primer composition, the polyvalent metal ion (Al ion) concentration, the adhesive strength to the prosthesis made of a cured resin, and The storage stability was measured and the results are shown in Table 1.
In Table 1, X is a value indicating the amount of polyvalent metal ions per gram of component (A).

<Examples 2-4, Comparative Examples 1-2>
A two-part primer composition was prepared in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and the primer composition was evaluated in the same manner. The results are shown in Table 1. It was.

  In Examples 1 to 4, each component was formulated so as to satisfy the constitution of the primer composition of the present invention. In any case, excellent adhesive strength and storage with respect to the cured dental resin were obtained. It turns out that it has stability.

  On the other hand, the component (B) is not blended in the comparative example 1, and the component (A1) is not blended in the comparative example 2, and the adhesive strength of the dental resin cured body is very high in any case. It was low.

<Example 5>
The following prescription:
Acidic group-containing polymerizable monomer (A1): 2.5 g of PM
Polymerizable monomer (A2): 3.0 g of BisGMA, 2.0 g of 3G, 2.5 g of HEMA
Polyvalent metal ion (B) source: 1.2 g aluminum triisopropoxide Volatile organic solvent (C): 8.5 g isopropanol (IPA)
Water (D): 1.5 g of distilled water Other components: 0.003 g of BHT (polymerization inhibitor)
According to the above, the above-mentioned components were mixed with stirring to prepare a one-component primer composition. In addition, about this primer composition, the polyvalent metal ion (Al ion) density | concentration, the adhesive strength with respect to the prosthesis made from resin hardened | cured material, and storage stability were measured, and the result was shown in Table 3.
In Table 3, X is a value indicating the amount of polyvalent metal ions per gram of component (A).

<Examples 6 to 28>
A primer composition was prepared in the same manner as in Example 5 except that the formulation was changed as shown in Table 2, and the primer composition was evaluated in the same manner. The results are shown in Table 3.

<Comparative Example 3>
A primer composition was prepared in the same manner as in Example 5 except that no polyvalent metal ion (B) supply source was added, and the primer composition was evaluated in the same manner. The results are shown in Table 5. Indicated.

<Comparative Examples 4-5>
A primer composition was prepared in the same manner as in Example 5 except that the formulation was changed as shown in Table 4, and the primer composition was evaluated in the same manner. The results are shown in Table 5.

<Reference Examples 1-4>
A primer composition was prepared in the same manner as in Example 5 except that the formulation was changed as shown in Table 4, and the primer composition was evaluated in the same manner. The results are shown in Table 5.

  In Examples 5 to 28, each component was formulated so as to satisfy the configuration of the one-component primer composition of the present invention, and in any case, excellent adhesion to the cured dental resin was achieved. It can be seen that it has strength and storage stability.

  On the other hand, the component (B) is not blended in Comparative Example 3, the component (A1) is not blended in Comparative Example 4, and the content of the component (A1) in Comparative Example 5 is that of the present invention. In any case, the adhesive strength to the cured dental resin was very low.

  Reference Example 1 was a case where the amount of ions was less than the range of the present invention, and the adhesive strength was not sufficient. In Reference Examples 2 and 3, the compounding amount of the volatile organic solvent as the C component is the condition shown in the present invention (when the amount of metal ions eluted from the component B is Xmeq, the compounding amount is 20 × X parts by mass or more. ), But the adhesive strength immediately after preparation was good, but the primer composition gelled after 1-5 days after standing at 37 ° C. In Reference Example 4, the compounding amount of the volatile organic solvent as component C was blended in an amount exceeding the conditions (30 to 150 parts by mass) indicated in the present invention, and sufficient adhesive strength was not obtained. .

<Production example 1>: Production of polyvalent metal filler MF1 Fluoroaluminosilicate glass powder (Tokuso ionomer, manufactured by Tokuyama Dental Co.) was averaged using a wet continuous ball mill (New My Mill, manufactured by Mitsui Mining Co., Ltd.). After grinding to a diameter of 0.5 μm, 1 g of the obtained powder is treated with 20 g of 5.0 N hydrochloric acid, and the particle surface is treated for 40 minutes to obtain a polyvalent metal filler (polyvalent metal ion-eluting filler) MF1. Obtained.
0.1 g of the obtained polyvalent metal filler MF1 was immersed and held in 10 ml of a 10 wt% maleic acid aqueous solution at a temperature of 23 ° C. for 24 hours, and the amount of the eluted polyvalent metal ion was emitted by ICP (inductively coupled plasma) emission. As a result of analysis using spectroscopic analysis, the amount of ions eluted for 24 hours of this polyvalent metal filler MF1 was 10 meq / g-filler (Al ³⁺ = 6.7, La ³⁺ = 2.8, Ca ²⁺ = 0. 5).

<Production Example 2>: Production of polyvalent metal filler MF2 A polyvalent metal filler MF2 was obtained in exactly the same manner as in Production Example 1, except that the treatment time with 5.0N hydrochloric acid was 20 minutes. As a result of ICP emission spectroscopic analysis, the amount of ions eluted for 24 hours of this polyvalent metal filler MF2 was 25 meq / g-filler (Al ³⁺ = 16.7, La ³⁺ = 6.9, Ca ²⁺ = 1.4). .

<Production Example 3>: Production of polyvalent metal filler MF3 A polyvalent metal filler MF3 was obtained in exactly the same manner as in Production Example 1 (or Production Example 2) except that no treatment with hydrochloric acid was performed. As a result of ICP emission spectroscopic analysis, the amount of ions eluted for 24 hours of this polyvalent metal filler MF3 was 50 meq / g-filler (Al ³⁺ = 33.4, La ³⁺ = 14.0, Ca ²⁺ = 2.6). .

<Example 29>
The following prescription:
Acidic group-containing polymerizable monomer (A1): 3.0 g of PM
Polymerizable monomer (A2): 2.4 g of BisGMA, 1.6 g of 3G, 3.0 g of HEMA
Multivalent metal ion (B) supply source: Multivalent metal ion-eluting filler MF1 (1.5 g) prepared in Production Example 1
Volatile organic solvent (C): 8.5 g of isopropanol (IPA)
Water (D): 2.0 g of distilled water Other components: 0.003 g of BHT (polymerization inhibitor)
According to the above, the above-mentioned components were mixed with stirring to prepare a one-component primer composition. With respect to this primer composition, the polyvalent metal ion concentration, the adhesive strength with respect to the prosthesis made of a cured resin, and the storage stability were measured, and the results are shown in Table 7.
In Table 7, X is a value indicating the amount of polyvalent metal ions per gram of component (A).

<Examples 30 to 40>
A primer composition was prepared in the same manner as in Example 29 except that the formulation was changed as shown in Table 6, and the primer composition was evaluated in the same manner. The results are shown in Table 7.

  In Examples 29 to 40, each component was blended so as to satisfy the configuration of the one-component primer composition of the present invention. In any case, excellent adhesion to the cured dental resin was achieved. It can be seen that it has strength and storage stability.

<Application Experiment Example 1>
MTU-6 was prepared as a sulfur-based monomer, which was dissolved in an organic solvent (IPA) to prepare a compatible extended primer assistant having 1% by mass of MTU-6.
The above primer assistant was added to the primer composition prepared in Example 5 so that MTU-6 was 1% by mass per polymerizable monomer (A), and a diverted primer was prepared (compatibility) An equal mass of the primer composition prepared in Example 5 and the extended primer assistant was collected).
Using this diverted primer, the adhesive strength for a cured resin prosthesis, a base metal alloy prosthesis, and a noble metal prosthesis was measured, and the results are shown in Table 8.

<Application Experiment Example 2>
A silane coupling agent (MPS) was used, and this was dissolved in an organic solvent (IPA) to prepare a compatible extended primer assistant having an MPS of 4% by mass.
The primer assistant was added to the primer composition prepared in Example 5 so that the MPS was 4% by mass per polymerizable monomer (A) to prepare a diversion primer.
Using this diverted primer, the adhesive strength to a cured resin prosthesis, a base metal alloy prosthesis, and a ceramic prosthesis was measured, and the results are shown in Table 8.

<Application Experiment Example 3>
MTU-6 as a sulfur monomer and MPS as a silane coupling agent are prepared and dissolved in an organic solvent (IPA). MTU-6 and MPS are 1% by mass and 4% by mass, respectively. Primer auxiliaries were prepared.
The above primer assistant was added to the primer composition prepared in Example 5 so that MTU-6 and MPS were 1% by mass and 4% by mass, respectively, per polymerizable monomer (A), and diverted. Primers were prepared (equal masses of the compatible extended primer assistant and the primer composition prepared in Example 5 were collected).
Using this diverted primer, the adhesive strength for a cured resin prosthesis, a base metal alloy prosthesis, a noble metal prosthesis, and a ceramic prosthesis was measured, and the results are shown in Table 8.

  In the application example 1, since the extended primer which mix | blended MTU-6 was used, the favorable adhesive strength with respect to resin, a base metal alloy, and a noble metal alloy prosthesis was obtained. In the application example 2, since the extended primer which mix | blended MPS was used, the favorable adhesive strength with respect to resin, a base metal alloy, and the ceramic prosthesis was obtained. Moreover, in the application example 3, since the extended primer which mix | blended both MTU-6 and MPS was used, favorable adhesive strength was obtained with respect to any prosthesis.

Claims (10)

(A) a polymerizable monomer component containing 5% by mass or more of an acidic group-containing polymerizable monomer;
(B) a polyvalent metal ion;
(C) The boiling point at 760 mmHg is 100 ° C. or lower, and the vapor pressure at 20 ° C. is
A volatile organic solvent of 1.0 KPa or higher ;
(D) water;
A primer composition for treating the surface of a dental prosthesis made of a cured resin, characterized by comprising: The amount of the polyvalent metal ion (B) is such an amount as to be 1.0 to 7.0 meq per 1 g of the polymerizable monomer component (A),
The volatile organic solvent (C) is added in an amount of 30 to 100 parts by mass per 100 parts by mass of the polymerizable monomer component (A).
Containing in the range of 150 parts by weight,
While containing the water (D) in an amount of 3 to 30 parts by mass per 100 parts by mass of the polymerizable monomer component (A),
The primer composition according to claim 1, wherein the components are mixed and stored in one package as one liquid. The volatile organic solvent (C) is represented by the following formula (I):
α ≧ 20 · X (I)
In the formula, α is the polymerizable monomer component (A) of the volatile organic solvent (C).
It is a blending amount per 100 parts by mass,
X is a polyvalent metal ion (B) per 1 g of the polymerizable monomer component (A).
Is a number indicating the amount (meq) of
The primer composition of Claim 2 contained in the quantity which satisfies the conditions represented by these.   The primer composition according to claim 2, wherein the polyvalent metal ion (B) is present by elution from a polyvalent metal ion-eluting filler.   The polyvalent metal ion-eluting filler has a polyvalent metal ion elution amount of 5.0 to 500 meq / g- when 0.1 g of the filler is added to 10 ml of a 10 wt% aqueous maleic acid solution and held at 23 ° C. for 24 hours. The primer composition according to claim 4, which shows a filler.   The primer composition according to claim 4, wherein the polyvalent metal ion-eluting filler is a powder having an average particle size of 0.01 to 5 μm.   The primer composition according to claim 1, wherein the acidic group-containing polymerizable monomer in the polymerizable monomer component (A) is a polymerizable monomer containing a phosphate group. Further, (E) a polyvalent metal ion non-releasing inorganic filler is added to the polymerizable monomer component (A).
The primer composition according to claim 1, comprising 2 to 20 parts by mass per 100 parts by mass.   The primer composition according to claim 1, further comprising (F) a photopolymerization initiator. A package primer composition according to claim 2 is contained, conformity extended primer aid composed of an organic solvent as well as a sulfur atom-containing polymerizable monomer and / or a silane coupling agent is contained Package and
The organic solvent is a volatile organic solvent having a boiling point at 760 mmHg of 100 ° C. or lower and a vapor pressure at 20 ° C. of 1.0 KPa or higher.
Dental prosthesis in which the sulfur atom-containing polymerizable monomer is at least one selected from the group consisting of a radical polymerizable compound that generates a mercapto group by tautomerism, a radical polymerizable disulfide compound, and a radical polymerizable thioether compound Primer kit.