JP6130176B2 - Dental restoration kit - Google Patents

Description

The present invention relates to a dental kit comprising a filling restoration material filled in a cavity portion of a tooth and a pretreatment agent used for firmly bonding and fixing the filling restoration material to a tooth in the dental field. It is.

  When the dental cavities are damaged due to caries or the like, and the cavity is relatively small due to damage, generally, a polymerizable material called a filling restoration material or a composite resin is used from the viewpoint of aesthetics, simplicity of operation, and speed. It is used.

By the way, since the filling restoration material does not have adhesiveness to the tooth, an adhesive made of a polymerizable composition is used, and the adhesive is applied to the cavity portion where the filling restoration material is applied and cured. A means for adhering the filling and restorative material to the tooth by means of applying the filling and restorative material thereon and curing it has been adopted.
The polymerizable composition used as such an adhesive usually includes a methacrylate monomer as a main component polymerizable monomer, and is designed to be polymerized and cured by photopolymerization. , Its adhesive strength to the tooth is not enough. That is, when a filling restorative material is applied and cured on a cured product of such an adhesive material, the shrinkage of the filling restorative material is large, and a large tensile stress is generated at the interface between the filling restorative material and the adhesive material. In order to improve the adhesive strength, various means have been proposed in order to improve the adhesive strength.

As a means for increasing the adhesive strength of the filling restorative material to the tooth, the most popular one is to use a pretreatment agent (primer). The pretreatment agent contains an acid component that etches the tooth and further penetrates into the tooth. After the pretreatment agent is applied to the cavity of the tooth, the above-described adhesive is applied, Furthermore, a filling restoration material is applied thereon.
Recently, Patent Documents 1 and 2 have proposed an adhesive composition in which an acidic group-containing polymerizable monomer coexists with water for the purpose of omitting the work with a pretreatment agent.
In such an adhesive composition, an acidic group-containing polymerizable monomer has a function as a primer, and polymerization and curing is performed in a state in which the monomer penetrates into the tooth, and a filling restoration is performed thereon. The material is applied and polymerization hardening is performed. According to such a technique, since the adhesive composition also serves as a pretreatment agent, the work of applying the pretreatment agent can be omitted, not only the operation can be simplified, but also the adhesion strength to the tooth can be improved. It can be done.
However, even when such an adhesive composition is used, there remains a problem of a decrease in adhesive strength due to a large polymerization shrinkage of the filling and restorative material.

Further, a technique in which the bonding operation is further simplified has been proposed. For example, Patent Document 3 discloses (a) an acidic group-containing radical polymerizable monomer, (b) a fourth period transition metal compound, and (c). Pretreatment agent (A) containing water, (d) radical polymerizable monomer having no acidic group, (e) organic peroxide, (f) photopolymerization initiator, and (g) silica-based inorganic filler A dental filling / restoration kit consisting of a filling / restoring material (B) containing the above has been proposed by the present applicant.
In this filling / restoration kit, after applying the pretreatment agent, the filling / restoring material is applied, and by light irradiation, the pretreatment agent and the filling / restoring material are polymerized and cured in one step. Has been simplified. Moreover, in this case, since the transition metal compound blended in the pretreatment agent and the organic peroxide blended in the filling restoration material function as a radical polymerization initiator, the pretreatment agent and the filling restoration material In the vicinity of the interface, chemical polymerization also proceeds with photopolymerization, and as a result, the adhesive strength of the filling and restorative material is increased.
However, even with such a technique, the problem of decrease in adhesive strength due to large polymerization shrinkage of the filling restoration material has not been completely solved.

On the other hand, Patent Document 4 proposes a dental material containing a polycyclic allyl sulfide having a very special heterocyclic structure as a monomer, and this dental material can be used as a filling restorative material.
In this dental material, polymerization shrinkage is relaxed and high adhesive strength can be expected. However, a very special monomer has to be used, and there is a drawback that the monomer type is limited. Furthermore, although the polymerization shrinkage has been relaxed, there is also a drawback that the cured product becomes loose and causes a decrease in strength, so that the problem due to the polymerization shrinkage has not yet been fundamentally solved. Is the current situation.

JP 2004-352698 A JP-A-9-263604 JP 2009-167132 A JP 2007-222402 A

  Therefore, an object of the present invention is to include a pretreatment agent and a dental restoration material, and can perform adhesion and fixation of the dental restoration material to the cavity of the tooth with a simple operation, and at the same time, when the dental restoration material is cured. To provide a dental restoration kit and a method for curing a dental restorative material that can effectively avoid a decrease in adhesive strength due to polymerization shrinkage and can form a high-strength cured product (that is, a restorative material) It is in.

According to the present invention, a radically polymerizable monomer (a1) containing an acidic group-containing radically polymerizable monomer, a pretreatment agent (A) containing water (a2) and a water-soluble organic solvent (a3), a radical In a dental restoration kit comprising a filling restorative material (B) containing a polymerizable monomer (b1), an inorganic filler (b2) and a photopolymerization initiator (b3),
An organic halogen compound which functions as an atom transfer radical polymerization initiator, an organometallic compound which functions as an atom transfer radical polymerization catalyst, are blended separately from each other in the pre-treatment agent (A) and filler repair material and (B) And a dental restoration kit characterized in that the organometallic compound is a transition metal complex .

In the dental restoration kit of the present invention,
(1) The organic halogen compound is 100 parts by mass of the polymerizable monomer (a1) or (b1) contained in the pretreatment agent (A) or the filling / restoring material (B) in which the compound is blended. per 5-30 are blended in an amount of parts by weight, the organometallic compound, the filling repairing material to which the compound is blended (B) or the polymerizable monomer contained in the pretreatment agent (a) The body (b1) or (a1) is blended in an amount of 3 to 20 parts by mass per 100 parts by mass,
(2) The organohalogen compound is blended in the filling restoration material (B), and the organometallic compound is blended in the pretreatment agent (A).
(3) The organic halogen compound is represented by the following formula (1):
> C (X) -CO- (1)
Wherein X is a halogen atom selected from chlorine, bromine and iodine.
Or a compound having a carbonyl structure represented by the following formula (2):
_{CH 2 = C (Rx) -CO-} (2)
In the formula, Rx is a group having a halogen atom selected from chlorine, bromine and iodine as a substituent.
A compound having an acrylic structure represented by :
Is preferred.

  The present invention uses atom transfer radical polymerization to relieve the stress generated at the interface between the pretreatment agent (A) and the filling restorative material (B) due to polymerization shrinkage of the filling restorative material (B). In order to effectively suppress a decrease in adhesive strength due to shrinkage, an organic halogen compound that functions as an atom transfer radical polymerization initiator and an organometallic compound that functions as an atom transfer radical polymerization catalyst are treated with the treatment described above. It is characterized in that the agent (A) and the filling / restoring material (B) are blended separately.

次いで、このラジカル（Ｒ・）がモノマー（Ｍ）を取り込んで成長する反応と、モノマーを取り込んだ成長ラジカルがハロゲンを取り込んだ高原子価状態の金属種［Ｃｕ(II)−Ｘ］と反応して再び低原子化状態の金属種［Ｃｕ(I)］を生成する疑似停止反応とが可逆的に進行していく。この過程は、次式で表される。

このように進行する重合は、原子移動ラジカル重合として知られている。 That is, atom transfer radical polymerization is a form of living polymerization and proceeds as follows.
First, an organohalogen compound that functions as an initiator and an organometallic compound that functions as a catalyst (in a low valence state) react to extract a halogen from the organohalogen compound, generating a radical and a metal species in a high valence state. To do. This process is represented by the following formula, when the organic halogen compound is represented by RX (X is halogen), the low-valence organic metal compound is represented by Cu (I), and the high-valence metal species is represented by Cu (II). The

Next, this radical (R.) takes in the monomer (M) and grows, and the radical that takes in the monomer reacts with a high-valence metal species [Cu (II) -X] that takes in halogen. Then, the pseudo-stop reaction for generating the low-atom state metal species [Cu (I)] proceeds reversibly. This process is expressed by the following equation.

Polymerization that proceeds in this way is known as atom transfer radical polymerization.

  In the present invention, in the above atom transfer radical polymerization, the organohalogen compound functioning as an initiator and the organometallic compound functioning as a catalyst are blended separately into the treating agent (A) and the filling restorative material (B). Therefore, the stress generated at the interface between the pretreatment agent (A) and the filling / restoring material (B) due to polymerization shrinkage of the filling / restoring material (B) can be relaxed.

  Specifically, in order to repair a cavity formed in a tooth, first, a polymer component (a1) containing an acidic group-containing radical polymerizable monomer (hereinafter sometimes referred to as an acidic monomer) A pretreatment agent (A) containing water (a2) and a water-soluble organic solvent (a3) is applied to the cavity. As a result, the acidic monomer etches the tooth enamel and penetrates into the dentin. In such a state, a filling restorative material containing a normal radical polymerizable monomer (b1) (hereinafter sometimes simply referred to as a non-acidic monomer), an inorganic filler (b2), and a photopolymerization initiator (b3). (B) is filled on the pretreatment agent (A) applied to the cavity. Thereby, a part of non-acidic monomer (b1) in filling restoration material (B) permeates into pretreatment agent (A).

In the conventionally known means, photopolymerization is performed by irradiating light in this state, whereby the polymer component in the filling / restoring material (B) and the pretreatment agent (A) is polymerized, and the pretreatment agent (A ) To form a hardened body of the filling restorative material (B) joined to the cavity of the cavity, thereby restoring the tooth.
However, in the above case, since the polymerization shrinkage of the filling restorative material (B) is large, a large stress is generated at the interface between the pretreatment agent (A) and the filling restorative material (B). The strength is lowered, and in some cases, the cured filling / restoring material (B) is easily dropped off.
For example, as in Patent Document 3, a transition metal compound is blended with the pretreatment agent (A), and an organic peroxide is blended with the filling / restoring material (B), and the pretreatment agent (A) and the filling / restoration are performed. Even if a means of simultaneously proceeding photopolymerization and chemical polymerization in the vicinity of the interface with the material (B) is employed, the large polymerization shrinkage of the filling restoration material (B) cannot be sufficiently relaxed in the vicinity of the interface, It has not yet achieved a high bond strength to the tooth.

In contrast, in the present invention, the initiator (organohalogen compound) and the catalyst (organometallic compound) for atom transfer radical polymerization are distributed to the pretreatment agent (A) and the filling restoration material (B). Therefore, by applying the filling / restoring material (B) on the pretreatment agent (A) in the cavity, the initiator and the catalyst come into contact with each other at the interface portion, and the above-described atom transfer radical polymerization proceeds.
This atom transfer radical polymerization, unlike ordinary radical polymerization using an organic peroxide and a transition metal compound as in Patent Document 3 described above, proceeds slowly. That is, atom transfer radical polymerization starts from the time when the filling restorative material (B) is applied on the pretreatment agent (A), and a rubber-like polymer (or rubber-like polymerization by light irradiation in the subsequent operation) is started at the interface portion. A precursor to become a product. Therefore, after this, when photopolymerization by light irradiation is performed, a rubber-like polymer (or a precursor of the rubber-like polymer) is present at the interface portion between the pretreatment agent (A) and the filling / restoring material (B). As a result, the photopolymerization proceeds in a state of being generated, and as a result, the stress due to polymerization shrinkage of the filling restoration material (B) is relieved, and a decrease in adhesive strength due to such polymerization shrinkage is effectively suppressed, It becomes possible to ensure a large adhesive strength between the cured product of the filling restoration material (B) and the tooth substance.
In addition, normal radical polymerization as in Patent Document 3 is faster than atom transfer radical polymerization, and during irradiation with light, curing proceeds so that the interface portion does not exhibit rubber-like physical properties. This is considered to be a level that cannot withstand the polymerization shrinkage.

  In addition, in the present invention, the polymerization shrinkage of the filling restorative material (B) itself is not suppressed, so that the strength of the cured product of the filling restorative material (B) to be formed (that is, the tooth restoration material) is avoided. As with known means, a high-strength restoration material can be formed.

<Organic halogen compounds>
As understood from the above description, the organic halogen compound used in the present invention functions as a polymerization initiator in atom transfer radical polymerization. It is a compound that reacts rapidly and a halogen atom is withdrawn to generate a radical.

  Such organic halogen compounds are known per se, and various compounds are known. For example, some of these organic halogen compounds have one or more halogen atoms that define a polymerization initiation point at a portion where a halogen atom is extracted. Japanese Patent Application Laid-Open No. 2002-249505 discloses one having such a starting point and one having a plurality of starting points, but any organic halogen compound can be used in the present invention.

In the present invention, among various organic halogen compounds, the following formula (1):
> C (X) -CO- (1)
Wherein X is a halogen atom selected from chlorine, bromine and iodine.
A compound having a carbonyl structure represented by (hereinafter simply referred to as a halogen-substituted carbonyl compound) is preferably used.
That is, the carbonyl compound as described above has a halogen atom at the α position with respect to the carbonyl group (> C═O), and the halogen atom is activated. It reacts to extract a halogen atom and generate a radical.

Among the halogen-substituted carbonyl compounds as described above, those having two starting points, for example, the following formula (1-1);
> C (X) —CO—O—A—O—CO—C (X) <(1-1)
In the formula, X is a halogen atom described in the formula (1),
A is an alkylene group,
The one represented by is optimal. A typical halogen-substituted carbonyl compound represented by the formula (1-1) is ethylene bis (2-halogenoisobutyrate).

式中、Ｘは、式（１）に記載したハロゲン原子であり、
Ｙは、炭素数１〜８の非置換または置換アルコキシ基、或いは置換基を有して
いてもよいフェニル基であり、
Ｒ^Ａ及びＲ^Ｂは、それぞれ、水素原子または炭素数１〜８の非置換または置換
アルキル基である、
で表される化合物を挙げることでき、このようなハロゲン置換カルボニル化合物も好適に使用することができる。 Among the above halogen-substituted carbonyl compounds, those having one starting point include, for example, the following formula (1-2);

In the formula, X is a halogen atom described in the formula (1),
Y is an unsubstituted or substituted alkoxy group having 1 to 8 carbon atoms, or a phenyl group which may have a substituent,
R ^A and R ^B are each a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 8 carbon atoms,
And such halogen-substituted carbonyl compounds can also be preferably used.

In the present invention, the following formula (2):
CH ₂ = C (Rx) -CO-
In the formula, Rx is a group having a halogen atom selected from chlorine, bromine and iodine as a substituent.
The compound (halogen-substituted methacrylic compound) having an acrylic structure represented by general formula (1-1) is most preferred, similarly to the halogen-substituted carbonyl compound of formula (1-1). This halogen-substituted methacrylic compound has an unsaturated double bond in the molecule and functions as a monomer. As a result, the halogen-substituted methacrylic compound does not remain as an unreacted substance, and has not reacted with, for example, an organometallic compound as a catalyst. However, it is because it is polymerized with other monomers and incorporated into the cured product. Accordingly, such a halogen-substituted methacrylic compound has an advantage that it is not particularly necessary to strictly adjust the upper limit of the blending amount.

Examples of the group Rx of the halogen-substituted methacrylic compound of the above formula (2) include a halogenoalkyl group or a halogenoalkoxy group.
2- (2-bromoisobutyroxy) ethyl methacrylate,
2- (2-chloroisobutyroxy) ethyl methacrylate,
2- (2-iodoisobutyroxy) ethyl methacrylate,
Can be mentioned.

  The aforementioned organic halogen compound is blended in the pretreatment agent (A) or the filling / restoring material (B) so as to be separate from the organometallic compound described later. The blending amount is not so strict and cannot be generally defined, but generally, when blended in the pretreatment agent (A), the polymerizable monomer in the pretreatment agent (A) (A1) When blended in the filling / restoring material (B) in an amount per 100 parts by mass, the polymerizable monomer (b1) in the filling / restoring material (B) is 5 to 100 in an amount per 100 parts by mass. It is blended in an amount of 30 parts by weight, particularly 10 to 20 parts by weight. That is, if the pretreatment agent (A) or the filling / restoring material (B) is blended in such an amount, the pretreatment agent is used regardless of the amount of the pretreatment agent (A) or the filling / restoring material (B) applied. This is because the organic halogen compound can be present in a certain amount or more at the interface portion between (A) and the filling restorative material (B) to cause atom transfer radical polymerization at the interface portion.

In addition, regarding the amount of the organic halogen compound described above, when the organic halogen compound is a halogen-substituted methacryl compound, the methacryl compound is not included in the polymerizable monomer. This is because the reaction with the organometallic compound (radical generation by extraction of halogen) has priority over the polymerization reaction itself.
In the present invention, such an organic halogen compound is most preferably blended in the filling / restoring material (B) described later.

<Organic metal compound>
The organometallic compound used in the present invention functions as a polymerization catalyst in atom transfer radical polymerization, and reacts quickly with the organic halogen compound functioning as the polymerization initiator described above to extract a halogen atom. As can be understood from the reaction process of atom transfer radical polymerization, a low valence state and a high valence state can be reversibly transferred.
Therefore, as such an organometallic compound, a complex having a transition metal as a central metal can be used. Such transition metal complexes are well known as disclosed in, for example, JP-A-2002-249505, and in the present invention, such known transition metal complexes can be used without any particular limitation. it can.

For example, the transition metal is a metal of group 3-12 of the 4th period of the periodic table, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), Iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc (Zn).
Moreover, as a ligand coordinated to the transition metal, those having N, O, P, S or the like as a coordination atom, for example, tris (pyridyl) amine, 2,2′-pipyridine, tetramethylethylenediamine, Typical examples include pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, 1,10-phenatroline, triphenylphosphine, tributylphosphine, and the like, as long as these ligands can coordinate to the transition metal. And having a substituent such as an alkyl group such as a methyl group.

  The organometallic compound described above is blended with the pretreatment agent (A) or the filling / restoring material (B) so as to be separated from the organohalogen compound described above. As in the case of the organometallic halogen compound, the blending amount thereof is not so strict and cannot be specified generally. However, when blended in the pretreatment agent (A), the polymerization in the pretreatment agent (A) is usually performed. The amount per 100 parts by mass of the polymerizable monomer (b1) in the filling restorative material (B) when blended in the filling restorative material (B) in an amount per 100 parts by weight of the polymerizable monomer (a1) And 3 to 20 parts by mass, particularly 7 to 12 parts by mass. That is, when used in such an amount, the interface portion between the pretreatment agent (A) and the filling / restoration material (B) is constant regardless of the amount of the pretreatment agent (A) or the filling / restoration material (B) applied. An organometallic compound can be present in an amount greater than the amount, and atom transfer radical polymerization at the interface portion can be caused.

In addition, the organometallic compound mentioned above should just exist in a predetermined quantity in an interface part in the state which the pretreatment agent (A) and the filling restoration material (B) contacted. Therefore, a transition metal compound (for example, chloride, bromide) and an organic compound (for example, an amine) serving as a ligand are mixed in the pretreatment agent (A) or the filling restorative material (B), and predetermined by the time of use. The complex can also be formed.
In the present invention, such an organometallic compound is preferably blended in the pretreatment agent (A) (that is, the organohalogen compound is blended in the filling / restoring material (B)).

<Pretreatment agent (A)>

  The pretreatment agent (A) used in the present invention comprises, as basic components, a radical polymerizable monomer (a1) containing an acidic group-containing radical polymerizable monomer, water (a2) and a water-soluble organic solvent (a3). In addition to this basic component, any one of the aforementioned organic halogen compound (atom transfer radical polymerization initiator) and organometallic compound (atom transfer radical polymerization catalyst) is blended.

Radical polymerizable monomer (a1);
In the present invention, the radical polymerizable monomer (a1) in the pretreatment agent (A) is a component used for curing by polymerization and imparting adhesiveness to the filling restorative material (B), also called a composite resin. However, in order to ensure etching property (decalcification property) to enamel and permeability to dentin, such a monomer (a1) includes an acidic group-containing radical polymerizable monomer (hereinafter simply referred to as acidic). (Referred to as monomer). That is, such an acidic monomer deeply penetrates into the tooth in the cavity, and as a result, high adhesive strength can be ensured.

  The above acidic monomer has a property that its aqueous solution or aqueous suspension exhibits acidity, and has at least one acidic group and radically polymerizable unsaturated group in one molecule.

The acidic group of the acidic monomer is not particularly limited as long as the above-described atom transfer radical polymerization is not inhibited. For example, a carboxyl group (—COOH) or an anhydride thereof, a sulfo group (—SO ₃ H), a phosphinico group {= P (═O) OH}, phosphono group {—P (═O) (OH) ₂ } and the like are typical.
Also, the radically polymerizable unsaturated group is not particularly limited and may be any known group. Specifically, (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, (meth) acryloylthio derivative group such as (meth) acryloyl group, vinyl group, allyl group, styryl group Etc. are exemplified.

The use of such an acidic monomer is known, and in the present invention, any of those detailed in, for example, JP-A-2009-167132 can be used. Particularly preferred acidic monomers are shown below.
In the exemplified compounds shown below, R ₁ , R ₁ ′ and R ₁ ″ each represent a hydrogen atom or a methyl group.

  In the present invention, the above-mentioned acidic monomers are used singly or in combination of two or more, but it is not necessary for all of the radical polymerizable monomers (a1) to be acidic monomers. It is used together with a radically polymerizable monomer having no acidic group (hereinafter referred to as a non-acidic monomer).

  For example, the acidic monomer may be contained in an amount of 5 parts by mass or more, particularly 10 to 80 parts by mass in 100 parts by mass of the total radical polymerizable monomer (a1). When this amount is small, the etching property and penetrability of the acidic monomer to the tooth are unsatisfactory, and the adhesive strength to the tooth is likely to be unsatisfactory. Moreover, even if an excessive amount of acidic monomer is used, an improvement in the adhesive strength beyond a certain level is not recognized, but the cost is rather increased.

  In addition, the non-acidic monomer used as the acidic monomer is usually used in this kind of pretreatment agent and is not limited to this, but in general, the following mono (meth) acrylate-based monomers are used. A monomer and a polyfunctional (meth) acrylate monomer are used singly or in combination of two or more.

1. Mono (meth) acrylate monomers;
Methyl (meth) acrylate Ethyl (meth) acrylate Glycidyl (meth) acrylate 2-Cyanomethyl (meth) acrylate Benzyl (meth) acrylate Polyethylene glycol mono (meth) acrylate Allyl (meth) acrylate 2-hydroxyethyl (meth) acrylate Glycidyl (meth) ) Acrylate 3-Hydroxypropyl (meth) acrylate Glyceryl mono (meth) acrylate 2- (meth) acryloxyethyl acetyl acetate

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) a Relate epoxy (meth) acrylate

  Non-acidic monomers include polymerizable monomers other than the above (meth) acrylate monomers, for example, fumaric acid ester compounds such as dimethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene, divinylbenzene Styrene derivatives such as α-methylstyrene and α-methylstyrene dimer; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate;

Water (a2);
In this invention, water is mix | blended with the radically polymerizable monomer (a1) containing the acidic monomer mentioned above.
That is, a certain amount of water is present in the oral cavity environment to which the pretreatment agent (A) is applied. However, if water is not blended, decalcification (etching) by the acidic monomer is insufficient and high. It becomes difficult to obtain adhesive strength.

  The amount of water in such a pretreatment agent (A) should be in the range of 3 to 150 parts by mass, particularly 5 to 100 parts by mass, per 100 parts by mass of the radical polymerizable monomer (a1). . If this amount is small, decalcification tends to be inadequate and the adhesive strength tends to be low, and the use of a larger amount of water than necessary may cause poor curing or reduce the workability of curing. I will let you. That is, the pretreatment agent (A) is applied to the cavity and then water is removed by air blow or the like, and then the filling restoration material (B) is applied and cured, but the pretreatment agent (A) This is because if a large amount of water is contained therein, it may be difficult to remove the water by air blow.

A water-soluble organic solvent (a3);
In the present invention, a water-soluble organic solvent is used in order to adjust the viscosity of the pretreatment agent (A) and to uniformly disperse the radical polymerizable monomer (a1) described above. This water-soluble organic solvent has a boiling point at 760 mmHg of 100 ° C. or lower and a vapor pressure of 1.0 KPa or higher at 20 ° C. in consideration of removability and solubility in water. Those having a solubility in water at 20 ° C. of 20 g / 100 ml or more are used.
Examples of such a volatile water-soluble organic solvent include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, and the like, and a plurality of these organic solvents can be used as necessary. It is. In general, ethanol, isopropyl alcohol and acetone are preferably used in consideration of toxicity to the living body.

The blending amount of such a water-soluble organic solvent varies depending on the type and amount of the radical polymerizable monomer (a1) used, but generally 2 to 400 parts per 100 parts by mass of the monomer (a1). Part by mass, particularly 5 to 100 parts by mass is preferred.
In addition, these water-soluble organic solvents are also removed by air blowing before applying the filling restoration material (B) when the adhesive composition of the present invention is applied to the tooth surface, similarly to the water.

Other compounding agents;
The pretreatment agent (A) described above may contain various compounding agents known in the dental field in addition to the components described above.
For example, a pH adjuster for maintaining the pH of the pretreatment agent (A) in a certain region and ensuring stable decalcification by the acidic monomer can be blended. For example, by adjusting the pH of the pretreatment agent (A) to 4.8 or less, particularly 0.5 to 4.0, particularly preferably 1.0 to 3.0 with a pH adjuster, the pretreatment is performed. The deashing effect of the agent (A) can be exhibited to the maximum, and high adhesive strength can be ensured.

  Typical examples of such pH adjusters include citric acid, tartaric acid, hydrofluoric acid, malonic acid, glycolic acid, lactic acid, phthalic acid, isophthalic acid, terephthalic acid, and methoxyacetic acid.

  The pH of the pretreatment agent (A) was mixed with ethanol at a concentration of 10% by mass to neutral phosphate pH standard solution (pH 6.86) and phthalate pH standard solution (pH 4. This is a value measured at 25 ° C. with a pH meter using a pH electrode calibrated in 01). Ethanol used for dilution may have a purity of 99.5% or higher, and the pH value of the ethanol alone may be 4.8 to 5.0.

  Moreover, in order to improve the storage stability of a pretreatment agent (A) and to prevent the gelatinization at the time of long-term storage, a polymerization inhibitor can also be mix | blended. Examples of such a polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and 2,6-ditertiary butyl cresol. The general blending amount of the polymerization inhibitor is such an amount that does not significantly affect the adhesive force and does not adversely affect the above-described atom transfer radical polymerization. Usually, the total polymerizable monomer (a1) The amount is 5 parts by mass or less, particularly about 0.001 to 1 part by mass per 100 parts by mass.

  In addition to the above, for example, a polyvalent ion-releasing filler such as fluorosilicate glass can be appropriately blended to form an ionic cross-link with the acidic monomer, thereby increasing the adhesive strength to the tooth, and other factors. Viscosity agents, ultraviolet absorbers, dyes, pigments and the like can be blended in amounts that do not cause polymerization inhibition.

  In the present invention, together with the various components described above, any one of the aforementioned organic halogen compound (atom transfer radical polymerization initiator) and organometallic compound (atom transfer radical polymerization catalyst) is blended, and a pretreatment agent (A ) Is used.

<Filling restoration material (B)>
In the filling / restoration kit of the present invention, the filling / restoring material (B) used together with the pretreatment agent (A) described above is also called a composite resin, and includes a radical polymerizable monomer (b1) and an inorganic filler (b2). And a photopolymerization initiator (b3) as an essential component.

Radical polymerizable monomer (b1);
This radical polymerizable monomer (b1) is the same as the non-acidic monomer described in the section of the pretreatment agent.
Preferably, a monomer having a methacryloyloxy group or an acryloyloxy group is used from the viewpoint of adhesion and ease of handling, and in particular, since it easily penetrates into the pretreatment agent (A), it is water-soluble and simple. Functional ones such as 2-hydroxyethyl (meth) acrylate are optimal.
From the viewpoint of adhesion durability, water-insoluble and multifunctional monomers are also suitable. For example, triethylene glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meta ) Acrylate, dipentaerythritol hexa (meth) acrylate, urethane di (meth) acrylate, 2,2-bis [4- (2-hydroxy-3- (meth) acryloxypropoxy) phenyl] propane, 2,2-bis ( 4- (Meth) acryloxyethoxyphenyl) propane and the like are also preferably used.
These radically polymerizable monomers (b1) (non-acidic monomers) may be used alone or in combination of two or more.

Inorganic filler (b2);
The inorganic filler (b2) in the filling / restoring material (B) is used to impart mechanical strength and water resistance to the cured product of the filling / restoring material (B). used.
Examples of the inorganic filler include fumed silica, silica other than fumed silica, zirconia, titania, silica / zirconia, silica / titania, and the like.
Further, such an inorganic filler may be surface-treated with a silane coupling agent in the same manner as known per se. That is, the inorganic filler can be hydrophobized by surface treatment to increase the affinity with the radical monomer (b1), thereby further improving the mechanical strength and water resistance.

  The blending amount of the inorganic filler is not particularly limited, but is generally 120 to 900 parts by weight, particularly 140, per 100 parts by weight of the radical monomer (b1) in the filling restorative material (B). A range of 600 parts by mass is preferable.

Photopolymerization initiator (b3);
In the filling restorative material (B), the radical polymer (b1) described above in the oral cavity and the radical polymerizable monomer in the pretreatment agent (A) are polymerized (photopolymerized) at an arbitrary timing. A polymerization initiator (b3) is blended.
As such a photopolymerization initiator (b3), 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.

In addition, tertiary amines, barbituric acids, mercapto compounds, and the like are used as the above-described polymerization accelerator. Specific examples thereof are as follows.
Tertiary amines;
N, N-dimethylaniline,
N, N-diethylaniline,
N, N-di-n-butylaniline,
N, N-dibenzylaniline,
N, N-dimethyl-p-toluidine,
N, N-diethyl-p-toluidine,
N, N-dimethyl-m-toluidine,
p-bromo-N, N-dimethylaniline,
m-chloro-N, N-dimethylaniline,
p-dimethylaminobenzaldehyde,
p-dimethylaminoacetophenone,
p-dimethylaminobenzoic acid,
p-dimethylaminobenzoic acid ethyl ester,
p-dimethylaminobenzoic acid amyl ester,
N, N-dimethylanthranic acid methyl ester,
N, N-dihydroxyethylaniline,
N, N-dihydroxyethyl-p-toluidine,
p-dimethylaminophenethyl alcohol,
p-dimethylaminostilbene,
N, N-dimethyl-3,5-xylidine,
4-dimethylaminopyridine,
N, N-dimethyl-α-naphthylamine,
N, N-dimethyl-β-naphthylamine,
Tributylamine,
Tripropylamine,
Triethylamine,
N-methyldiethanolamine,
N-ethyldiethanolamine,
N, N-dimethylhexylamine,
N, N-dimethyldodecylamine,
N, N-dimethylstearylamine,
N, N-dimethylaminoethyl acrylate,
N, N-dimethylaminoethyl methacrylate,
2,2 ′-(n-butylimino) diethanol and the like.
Barbituric acids;
5-butyl barbituric acid,
1-benzyl-5-phenylbarbituric acid and the like.
Mercapto compounds;
Dodecyl mercaptan,
Pentaerythritol tetrakis (thioglycolate), etc.

  The amount of such photopolymerization initiator (b3) is particularly limited as long as it is an effective amount that can cure the radical polymerizable monomer contained in the filling / restoring material (B) or the pretreatment agent (A). However, it is generally set in the range of 0.01 to 10 parts by weight, particularly 0.1 to 5 parts by weight per 100 parts by weight of the radical polymerizable monomer (b3). Good.

Other compounding agents;
In the filling restorative material (B), in addition to the above-mentioned photopolymerization initiator (b3), an electron acceptor such as an iodonium salt, a trihalomethyl-substituted S-triazine, or a phenacylsulfonium salt compound may be blended. By blending such an electron acceptor, the polymerization activity can be increased.
Furthermore, like the pretreatment agent (A) described above, a polymerization inhibitor can be added to increase the storage stability, and if necessary, polymer compounds such as polyvinyl pyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, etc. It is possible to add organic thickeners. Moreover, various additives, such as a ultraviolet absorber, dye, an antistatic agent, a pigment, and a fragrance | flavor, can also be mix | blended as needed.

As described above, the filling / restoration material (B) in the filling / restoration kit of the present invention includes an organic halogen compound (atom transfer radical polymerization initiator) and an organometallic compound (atom transfer radical polymerization catalyst) in addition to the various components described above. ) Is blended. That is, when an organic halogen compound is blended in the pretreatment agent (A), an organometallic compound is blended in the inorganic filling restorative material (B), and an organometallic compound is blended in the pretreatment agent (A). In the case of blending, an organic halogen compound is blended in the inorganic filling / restoring material (B).
In the present invention, any of the embodiments can be adopted, but considering that the pH of the pretreatment agent (A) is on the acidic side, an atom can be obtained by adding a transition metal halide and a ligand. Since an organometallic compound (transition metal complex) that functions as a mobile radical polymerization catalyst is quickly generated, an organohalogen compound is blended in the filling restorative material (B), and an organometallic compound is blended in the pretreatment agent (A). It is preferable to adopt the embodiment.

<Use of dental filling restoration kit>
To perform dental restoration using the dental filling / restoration kit of the present invention, first, the above-mentioned pretreatment agent is applied to the cavity of the tooth to be restored, and then water and a water-soluble organic solvent are volatilized by air blow or the like. .
In this state, the filling restorative material (B) is applied on the pretreatment agent (A) applied in advance so as to fill the cavity of the tooth.

  As a result, the organic halogen compound (atom transfer radical polymerization initiator) or the organometallic compound (atom transfer radical polymerization catalyst) in the filling / restoring material (B) permeates into the pretreatment agent (A), and the interface between them. The portion comes into contact with the organometallic compound or the organic halogen compound in the pretreatment agent (A), and atom transfer radical polymerization starts at the interface portion between the two.

  When the atom transfer radical polymerization at the interface part proceeds to some extent and a rubber-like elastic body is formed, the radical polymerization property in the pretreatment agent (A) is started by irradiating light and starting photopolymerization. The monomer (a1) and the radical polymerizable monomer (b1) in the filling / restoring material (B) are polymerized. As a result, the pretreatment agent (A) and the filling restorative material (B) are completely cured, and the high-strength cured product of the filling restorative material (B) filling the cavities becomes a cured product of the pretreatment agent (A). And the cavity is repaired.

That is, although the polymerization shrinkage of the filling restorative material (B) is large, photopolymerization proceeds in a state where a rubber-like elastic body is formed by atom transfer radical polymerization at the interface portion with the pretreatment agent (A). The stress due to the shrinkage is relieved at the interface portion, and as a result, the peeling of the cured product of the filling restoration material (B) at the interface portion due to the large polymerization shrinkage is effectively avoided, and the strong adhesion strength to the cavity of the cavity is obtained. It is possible to ensure the thickness.
There is no problem as long as the timing of light irradiation is within the range of normal clinical operation.
For example, in clinical operation, even if light irradiation is performed immediately after holding the filling / restoring material (B) and holding the light irradiator, no problem occurs. That is, the atom transfer radical polymerization at the interface portion starts from when the filling / restoring material (B) is filled, and the radical generated by light irradiation by the metal halogen compound such as CuBr ₂ generated by atom transfer radical polymerization is also living radical polymerization. Shows the behavior. As a result, radical polymerization proceeds in a state where a rubber-like elastic body is formed at the interface, and the stress at the interface portion due to polymerization shrinkage is effectively relieved.
On the other hand, it takes several tens of minutes from the start of polymerization (immediately after filling the filling and restorative material (B)) to cure the interface portion to such an extent that the interface does not exhibit rubber elasticity by atom transfer radical polymerization. However, it is not possible to leave the patient for several tens of minutes after filling the filler (B) and do not perform light irradiation in normal clinical operation. Therefore, in the case of normal clinical operation, there is no fear of performing light irradiation after the effect at the interface portion has progressed too much.

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 materials, abbreviations, and test methods used in the following experiments are as follows.

[Non-acidic monomer]
Bis-GMA:
2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane D-2,6E:
2,2, -bis [(4-methacryloyloxypolyethoxyphenyl) propane]
3G: Triethylene glycol dimethacrylate 14G: Tetradecaethylene glycol dimethacrylate UDMA: Urethane dimethacrylate HEMA: 2-hydroxyethyl methacrylate

[Acid group-containing polymerizable monomer]
PM:
Mixture MDP of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate:
10-methacryloxydecyl dihydrogen phosphate MAC-10:
11-methacryloyloxy-1,1-undecanedicarboxylic acid

[Photopolymerization initiator component]
CQ: camphorquinone DMBE: ethyl 4-dimethylaminobenzoate DMPT: N, N-dimethylamino-p-toluidine BTPO: bis (2,6-dimethylbenzoyl) diphenylphosphine oxide TPO: 2,6-dimethylbenzoyldiphenylphosphine oxide

[Polymerization inhibitor]
HQME: Hydroquinone methyl ether BHT: Dibutylhydroxytoluene

[Organic solvent]
Isopropyl alcohol (IPA)
acetone

[Organic halogen compounds] (Atom transfer radical polymerization catalyst initiator)
BEMA: 2- (2-bromoisobutyroxy) ethyl methacrylate EBB: ethylene bis (2-bromoisobutyrate)
CEMA: 2- (2-chloroisobutyroxy) ethyl methacrylate IEMA: 2- (2-iodobutyroxy) ethyl methacrylate

[Organometallic compound component (atom transfer radical polymerization catalyst component)
CuBr: Copper (I) bromide
FeBr ₂ : Iron (II) bromide
TPMA: Tris (2-pyridylmethyl) amine HMTETA: 1,1,4,7,10,10-hexamethyltriethylenetetramine TPP: Triphenylphosphine

[Inorganic filler]
F1:
Spherical silica zirconia (average particle size 0.4 μm) hydrophobized with γ-methacryloyloxypropyl trimethoxysilane and spherical silica-titania (average particle size 0.08 μm) treated with γ-methacryloyloxypropyltrimethoxy Mixture of hydrophobized silane and mass ratio 70:30

<Bending strength>
A dental light irradiator (Toxo Power Light), filled with a restoration material in a stainless steel mold and pressed with polypropylene, changing the location so that the entire surface is exposed to light 30 seconds x 3 times. , Manufactured by Tokuyama Dental Co., Ltd.) and irradiated with light. Subsequently, it was made to contact | adhere to a polypropylene similarly from the opposite surface, and 30 seconds x3 times were irradiated with light, and the hardening body was obtained.
After immersing the test piece produced by the above method in water at 37 ° C. for 24 hours, the cured body was prepared into a 2 × 2 × 25 mm prismatic shape with # 800 water-resistant abrasive paper, and this was tested with a tester (Shimadzu Corporation). (Manufactured by Autograph AG5000D), and the three-point bending fracture strength was measured at a fulcrum distance of 20 mm and a crosshead speed of 1 mm / min.
Five test pieces were measured per test, and the average value was defined as the bending strength.

<Adhesive strength>
Within 24 hours after slaughter, the anterior teeth of the bovine mandible were removed, and the enamel or dentin plane was cut out under water injection so as to be parallel to the lip surface with # 800 emery paper (water-resistant abrasive paper). Next, compressed air was blown onto these surfaces for about 10 seconds to dry them, and then a double-sided tape having a hole with a diameter of 3 mm was fixed to this plane to define the bonding area. Next, a simulated cavity was produced by pasting 1.5 mm thick wax with 8 mmφ holes so as to be concentric with the double-sided tape.
A pretreatment material was applied to the simulated cavity, left for 20 seconds, and then dried with compressed air.
After drying, filling the restoration material into the simulated cavity and covering it with a cover glass, then using a dental light irradiator (Powerlight manufactured by Tokuyama Dental Co., Ltd.) for 30 seconds to polymerize and cure, Finally, the slide glass and wax were carefully removed to obtain a test piece.
In addition, when the photoinitiator is mix | blended in the pretreatment agent (pretreatment agent P11 which will be described later), the pretreatment agent is irradiated with light for 20 seconds before filling with the restoration material. The treating agent was cured.
After the test piece produced by the above method was immersed in water at 37 ° C. for 24 hours, a metal jig was attached, and a tensile tester (Shimadzu Autograph AG5000) was used and the crosshead speed was 2 mm / min. A tensile test was conducted to measure the adhesion strength to the enamel plane and the dentin plane.
In addition, five test specimens were measured per test, and the average value was defined as the bond strength.

(1) Preparation of dental pretreatment material A monomer solution having the following formulation was prepared.
PM (acidic monomer): 5.0 g
HEMA (non-acidic monomer): 5.0 g
Water: 2.0g
Acetone: 8.5g
In the above monomer solution,
CuBr / TPMA complex (atom transfer radical polymerization catalyst): 0.9 g
BHT (polymerization inhibitor): 0.003 g
Was dissolved to obtain a uniform dental pretreatment solution. This was designated as pretreatment material P1.
The CuBr / TPMA complex was obtained by dissolving 5.0 g of CuBr and 10.0 g of TPMA in 200 ml of DMF, stirring this solution for 10 minutes, and then removing DMF.
Moreover, as shown in Table 1, the pretreatment except that the formulation of the monomer solution, the type and amount of the atom transfer radical polymerization catalyst added to the monomer solution were changed, or the compounding agent added instead of the atom transfer radical polymerization catalyst was changed Pretreatment agents P2 to P12 were prepared in the same manner as agent P1.

(2) Preparation of Filling Restoration Material Each component was mixed according to the following formulation and stirred in the dark until uniform, to prepare a matrix.
Bis-GMA (non-acidic monomer): 6.0 g
3G (non-acidic monomer): 3.0 g
14G (non-acidic monomer): 1.0 g
EBB (organohalogen compound): 1.5 g
CQ (photopolymerization initiator): 0.05 g
DMBE (photopolymerization initiator); 0.05 g
HQME (polymerization inhibitor): 0.01 g
BHT (polymerization inhibitor): 003 g
Into the obtained matrix, spherical silica zirconia (F1) as an inorganic filler was mixed in an agate mortar so as to have a weight ratio of 39:61, and defoamed under vacuum to obtain a filling restoration material CR1.
Moreover, as shown in Table 2, filling restoration materials CR2 to CR10 were prepared in the same manner as above except that the composition of the matrix and the blending amount of the inorganic filler were changed.

<Example 1-13 and Comparative Examples 1-8>
Pretreatment agents P1 to P12 prepared above and filling restoration materials CR1 to 10 were used in combination as shown in Table 3, and the bending strength and the adhesion strength to enamel and dentin were measured for each. . The results are also shown in Table 3.

From the above experimental results, the initiator component and the catalyst component for radical transfer polymerization were mixed separately into the pretreatment agent (A) and the filling restorative material (B), and filled with the filling restorative material (B). Occasionally, the pre-processing agent (a) and the filling repairing material (B) and the onset Ming atom transfer radical polymerization at the interface portion is designed to start (example 1-13), machine of the cured product Stress is effectively relieved at the interface between the pretreatment agent (A) and the filling restorative material (B), while effectively ensuring the mechanical strength, and adhesion to the dentine (enamel and dentin) It can be seen that the strength is increased.

Claims (4)

A radically polymerizable monomer (a1) containing an acidic group-containing radically polymerizable monomer, a pretreatment agent (A) containing water (a2) and a water-soluble organic solvent (a3), and a radically polymerizable monomer ( In a dental restoration kit comprising b1), a filling restorative material (B) containing an inorganic filler (b2) and a photopolymerization initiator (b3),
An organohalogen compound that functions as an atom transfer radical polymerization initiator and an organometallic compound that functions as an atom transfer radical polymerization catalyst are blended separately in the pretreatment agent (A) and the filling restorative material (B). A dental restoration kit, wherein the organometallic compound is a transition metal complex.   The organic halogen compound is 5 to 100 parts by mass of the polymerizable monomer (a1) or (b1) contained in the pretreatment agent (A) or the filling / restoring material (B) containing the compound. The organometallic compound is blended in an amount of 30 parts by weight, and the polymerizable monomer (b1) contained in the filling / restoring material (B) or the pretreatment agent (A) in which the compound is blended. ) Or (a1) The dental restoration kit according to claim 1, which is blended in an amount of 3 to 20 parts by mass per 100 parts by mass.   The dental restoration kit according to claim 1 or 2, wherein the organic halogen compound is blended in the filling restorative material (B), and the organometallic compound is blended in the pretreatment agent (A). The organic halogen compound is represented by the following formula (1):
> C (X) -CO- (1)
Wherein X is a halogen atom selected from chlorine, bromine and iodine.
Or a compound having a carbonyl structure represented by the following formula (2):
CH2 = C (Rx) -CO- (2)
In the formula, Rx is a group having a halogen atom selected from chlorine, bromine and iodine as a substituent.
The dental restoration kit according to claim 1, which is a compound having an acrylic structure represented by the formula: