JP2007169224A - Tooth surface pre-treating material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tooth surface pre-treating material composition which can solve such a problem that high adhesive strengths have not been obtained by conventional techniques, even when dental adhesives are applied to bleached tooth dentins. <P>SOLUTION: This tooth surface pre-treating material composition for adhesion after bleached, containing a reducing compound to recover the adhesive force of the tooth surface bleached with a tooth bleaching agent containing at least one compound selected from the group consisting of organic peroxides, compounds producing hydrogen peroxide in aqueous solutions, and titanium dioxide, is characterized in that the reducing compound is at least one compound selected from the group consisting of sulfinic acid compounds, inorganic sulfite compounds, amine-based compounds and ammine complexes. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  It is related with the tooth surface pretreatment material composition for adhesion | attachment which can be adhere | attached with simple operation with respect to the tooth after bleaching. More specifically, the present invention relates to an adhesive tooth surface pretreatment material composition that is advantageously used as a surface coating material such as a tooth or as an adhesive with a dental restoration resin such as a PMMA resin, resin cement, or composite resin.

In recent years, the number of patients seeking improvement in the aesthetics of discolored and colored teeth is increasing due to the improvement of consciousness regarding aesthetics in the oral cavity. Conventionally, in order to improve these aesthetics, a treatment in which a certain amount of tooth is removed and replaced with an artificial object using a technique such as a crown prosthesis or a laminate veneer has been mainly performed.
However, with these treatments, many tooth structures are deleted only for aesthetic reasons, and since teeth are also a tissue that cannot be regenerated, the minimal intervention (minimum intervention) that has become a trend in recent dental treatments. This is incompatible with the concept of invasiveness.

In such a situation, the tooth bleaching method has come to be frequently used as an aesthetic recovery means that does not delete teeth at all.
However, when a bleaching agent is applied, there is a risk of causing a decrease in adhesive strength. As a pretreatment agent for treating the surface of such a tooth, Patent Document 1 discloses a treatment agent for the tooth surface comprising (A) a reducing inorganic compound containing sulfur and (B) an aqueous solvent. ing. Patent Document 2 discloses an adhesive primer composition for a tooth containing (A) a polymerizable monomer, (B) a reducing inorganic compound containing sulfur, and (C) an aqueous solvent. .

Furthermore, Patent Document 3 discloses a tooth surface pretreatment material set made of a reducing compound and an etching material.
The above publication shows that the adhesive strength is increased by bonding to the surface of the tooth treated with the sulfur-based reducing agent. In these publications, it is described that the sulfur-based reducing agent is preferably applied after etching. On the other hand, it has already been found that applying dental adhesives to tooth surfaces that have been pre-treated with a solution of sodium hypochlorite or an oxidizing compound such as hydrogen peroxide will result in a decrease in bond strength. By adjusting the dental surface treated with an oxidizing compound to a non-oxidizing state in this way, it is shown that the adhesive strength is not easily lowered when a dental adhesive is applied to such a surface. ing.
Regarding bonding to bleached enamel, Non-Patent Document 1, “Association of composite resin to bleached bovine enamel”, using ascorbic acid together with bonding to the tooth surface after bleaching There is a description that the adhesive strength has been recovered.

As a bleaching agent, bleaching is performed with a one-to-one mixture of hydrogen peroxide and sodium peroxoborate tetrahydrate, and camphorquinone and Mega-bond which is an amine polymerization initiator are used as a bonding material. As described above, in this announcement, the polymerization initiator is limited to a combination of camphorquinone and amine, and the initiator is a partial oxide of tributylboron (TBB-O / manufactured by Sun Medical Co., Ltd.), camphorquinone and sulfinic acid. No ternary polymerization initiators using benzoyl peroxide and amines, or ternary polymerization initiators using benzoyl peroxide, amines and sulfinic acid in combination were disclosed.
The present inventor has already obtained the knowledge that there is a risk of reducing the adhesive strength when an adhesive is applied to the tooth surface after the bleaching treatment, and thus the tooth surface treated with the tooth bleaching agent is obtained. By adjusting to a non-oxidizing state, it was found that when a dental adhesive is applied to such a surface, the adhesive strength is not easily lowered, and the present invention has been completed.
JP-A-6-40835 JP-A-6-40838 JP 2000-186010 A Japanese Journal of Prosthodontic Society 81st Annual Conference Abstracts, 81 pages

  Therefore, the object of the present invention is to eliminate the problem that the conventional technique may not be able to obtain a high adhesive strength even if a dental adhesive is applied to a tooth material that has been bleached. It is to provide a treatment material.

  Another object of the present invention is to provide a tooth surface pretreatment material for bonding with higher adhesive strength to a tooth surface that has already been bleached and whose surface is in an oxidizing state. It is in.

  According to the present invention, the above objects and advantages of the present invention include, firstly, at least one compound selected from the group consisting of an organic peroxide, a compound that generates hydrogen peroxide in an aqueous solution, and titanium dioxide. An adhesive tooth surface pretreatment material composition containing a reducing compound for recovering the adhesive force of a tooth surface bleached with a tooth bleaching agent, the reducing compound comprising sulfinic acids, inorganic sulfite And at least one compound selected from the group consisting of an amine compound and an ammine complex salt, and is achieved by a tooth surface pretreatment material composition for adhesion after bleaching.

  According to the present invention, the above objects and advantages of the present invention include, secondly, an organic peroxide, a compound that generates hydrogen peroxide in an aqueous solution, and at least one compound selected from the group consisting of titanium dioxide. An adhesive tooth surface pretreatment material composition containing a reducing compound for recovering the adhesive force of a tooth surface treated with a tooth bleaching agent, wherein the reducing compound is an ascorbic acid compound It is achieved by the adhesive tooth surface pretreatment material composition for bleaching after bleaching.

  According to the present invention, the above objects and advantages of the present invention are thirdly achieved by a kit comprising the pretreatment material composition for a tooth surface for adhesion after bleaching and a tooth bleaching agent of the present invention.

  According to the adhesive tooth surface pretreatment material composition of the present invention, the dental surface treated with the oxidizing compound is treated with the reducing compound to remove the influence of the oxidizing compound on the tooth surface, Since adhesion is performed using an adhesive, adverse effects such as a decrease in adhesion due to the oxidizing compound are unlikely to occur.

  Details of the present invention will be described below.

The present invention is a tooth surface pretreatment material that adheres with higher adhesive strength to the tooth surface after tooth bleaching treatment as described above.
The reducing compound used in the present invention is a reducing compound capable of reducing an oxidizing compound such as hydrogen peroxide, urea peroxide or peroxide, specifically, an organic reducing compound and There are inorganic reducing compounds.
A first aspect of the present invention is a tooth surface bleached with a tooth bleaching agent containing at least one compound selected from the group consisting of an organic peroxide, a compound that generates hydrogen peroxide in an aqueous solution, and titanium dioxide. An adhesive tooth surface pretreatment material composition containing a reducing compound for restoring the adhesive strength of the adhesive, wherein the reducing compound is selected from the group consisting of sulfinic acids, inorganic sulfites, amine compounds and ammine complex salts. It is a tooth surface pretreatment material composition for adhesion after bleaching, comprising at least one compound selected.

Examples of the sulfinic acid used as the reducing compound include benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalene. Mention may be made of aromatic sulfinic acids such as sulfinic acid or salts thereof.
Examples of inorganic sulfites used as the reducing compound include sulfite, bisulfite, metasulfite, metabisulfite, pyrosulfite, thiosulfuric acid, 1 dithionic acid, 1,2 thionic acid, hyposulfite, hydro Examples thereof include sulfur-containing inorganic reducing compounds such as sulfurous acid and salts thereof and sodium thiosulfate or salts thereof.

  Examples of amine compounds used as the reducing compound include N, N-dimethylaniline, N, N-dimethyl-p-toluidine (DMPT), N, N-diethyl-p-toluidine, N, N- Diethanol-p-toluidine (DEPT), N, N-dimethyl-p-tert-butylaniline, N, N-dimethylanisidine, N, N-dimethyl-p-chloroaniline, N, N-dimethylaminoethyl (meta) ) Acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobenzoic acid, and alkyl esters thereof, N, N-diethylaminobenzoic acid (DEABA) and alkyl esters thereof, N, N-dimethylaminobenzaldehyde Aromatic amines such as (DMABAd); N-phenylglycine (NPG) , N- tolyl glycine (NTG), N, N- (3--methacryloyloxy-2-hydroxypropyl), and the like phenylglycine (NPG-GMA).

Examples of ammine complex salts used as the reducing compound include compounds represented by the following formulae. In each formula, “X” independently represents a halogen atom, preferably a chlorine atom and / or a fluorine atom, and R independently represents an organic group.
[M ^I (NH ₃ )] X M ^I = Au, Cu
[M ^I (NH ₃ ) ₂ ] X M ^I = Li, Na, K, Cu, Ag, Au
[M ^II (NH ₃ )] X ₂ M ^II = Hg, Cu
[M ^I (NH ₃ ) ₃ ] X M ^I = Cu, Ag, Au
[M ^II (NH ₃ ) ₄ ] X ₂ M ^II = Be, Cu, Ca, Ba, Pd, Pt
[M ^IV (NH ₃ ) ₄ ] X ₄ M ^IV = Ti
[M ^II (NH ₃ ) ₂ X ₂ ] M ^II = Pd, Pt
[M ^II (NH ₃ ) ₃ X] X M ^II = Pd, Pt
R [M ^II (NH ₃ ) ₃ ] M ^II = Pd, Pt
[M ^I (NH ₃ ) ₆ ] X M ^I = Li, Na
[M ^II (NH ₃ ) ₆ ] X ₂ M ^II = Be, Mg, Ca, Zn, Cd, Cu, Mn, Fe, Co, Ni
[M ^III (NH ₃ ) ₆ ] X ₃ M ^III = Al, Ge, Tl, Ti, Cr, Co. Ru, Rh, Ir
[M ^IV (NH ₃ ) ₆ ] X ₄ M ^IV = Ti, Th, Ge, Pd, Pt
_{^{[M III (NH 3) 6}} X] X 2 M III = Cr, Co, Ru, Rh, Ir
[M ^IV (NH ₃ ) ₅ X] X ₃ M ^IV = Pt, Pd
[M ^III (NH ₃ ) ₄ X ₂ ] X M ^III = Cr, Co, Ru, Rh, Ir
[M ^IV (NH ₃ ) ₄ X ₂ ] X ₂ M ^IV = Pt, Pd
[M ^III (NH ₃ ) ₃ X ₃ ] M ^III = In, Bi, Cr, Co, Rh, As
R [M ^III (NH ₃ ) ₂ X ₄ ] M ^III = Co, Cr
R ₂ [M ^III (NH ₃ ) X ₅ ] M ^III = Co, Cr
R ₃ [M ^II (NH ₃ ) X ₅ ] M ^II = Fe
[M ^IV (NH ₃ ) ₄ X ₂ ] M ^IV = Pt, Pd
[M ^IV (NH ₃ ) ₄ X ₅ ] M ^IV = Pt
[M ^II (NH ₃ ) ₈ ] X ₂ M ^II = Ca, Sr
[M ^IV (NH ₃ ) ₈ ] X ₄ M ^IV = Zr

Among these ammine complex salts, M is a metal atom such as silver (Ag), iron (Fe), copper (Cu), calcium (Ca), potassium (K), and X is a halogen atom such as fluorine or chlorine. Of these compounds, silver diammine fluoride and calcium tetraammine difluoride are particularly preferable.
Examples of the organic peroxide used as the tooth bleaching agent include organic peracids such as urea peroxide, peroxy-t-butoxide, perbenzoic acid, and salts thereof.

Examples of the compound that generates hydrogen peroxide in the aqueous solution used as the tooth bleaching agent include hydrogen peroxide, perborate, percarbonate, persulfate, perphosphate, urea peroxide, and silicic acid. Examples thereof include inorganic peroxides such as sodium hydrogen peroxide adduct, calcium peroxide, and magnesium peroxide.
Examples of perborate include sodium perborate. Examples of the percarbonate include sodium percarbonate and potassium percarbonate. Examples of the persulfate include sodium persulfate and potassium persulfate. Examples of the superphosphate include sodium perphosphate. Of these, hydrogen peroxide, urea peroxide, and sodium perborate are preferable, and hydrogen peroxide and urea peroxide are particularly preferable.

The amount of hydrogen peroxide that can be supplied by a compound that generates hydrogen peroxide in an aqueous solution is preferably 0.5 to 10% by weight, more preferably 2 to 5% by weight, based on the composition. If the value falls below the lower limit of the numerical range, the bleaching effect is lowered, and if it exceeds the upper limit, there is a concern about harm to the living body, which is not preferable.
Further, the amount of hydrogen peroxide supplied by a compound that generates hydrogen peroxide in an aqueous solution is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, and used for tooth bleaching. If the value falls below the lower limit of the numerical range, the bleaching effect is lowered, and if it exceeds the upper limit, there is a concern about harm to the living body, which is not preferable.
The amount of hydrogen peroxide that can be supplied by the compound capable of supplying hydrogen peroxide in the aqueous solution or the amount of hydrogen peroxide to be supplied is a compound that supplies the hydrogen peroxide at a predetermined concentration in a closed system. Is the hydrogen peroxide concentration achieved by hydrogen peroxide that can be theoretically supplied.

The tooth bleaching agent may further contain titanium dioxide. In that case, a photocatalyst can further be contained. As the titanium dioxide, any titanium dioxide can be used regardless of its form and properties as long as it produces a photocatalytic action by light irradiation. Preferably, it is any one of anatase type, rutile type and brookite type, and rutile type is particularly preferable. Moreover, what improved affinity with the tooth surface can also be used by coating calcium phosphate on the surface of anatase type, rutile type and brookite type titanium dioxide. The coating preferably has an average film thickness of 0.1 to 500 nm.
The titanium dioxide is preferably in the form of fine particles, and the average particle diameter is preferably 0.1 to 500 nm, more preferably 0.5 to 200 nm, and still more preferably 1 to 100 nm. Furthermore, as the light causing the photocatalytic action, not only ultraviolet light having a wavelength of 380 nm or less but also visible light having a wavelength of 450 nm or more can be used.
The average particle diameter was measured in an ethanol solvent using a laser diffraction scattering method (measurement conditions: 250 ml of suspension liquid, 20 mg of measurement sample, within 5 minutes from sample dropping to completion of measurement).
Titanium dioxide is preferably contained in the tooth bleaching agent in an amount of 0.00001 to 10% by weight, more preferably 0.00001 to 5% by weight, and still more preferably 0.0001 to 2% by weight.

Examples of tooth bleaching agents include solutions / pastes containing hydrogen peroxide, compositions containing titanium dioxide and a compound that generates hydrogen peroxide in an aqueous solution (bleaching teeth based on the photocatalytic action caused by light irradiation). A composition containing titanium dioxide that generates a photocatalytic action by light irradiation, a compound that generates hydrogen peroxide in an aqueous solution, and a thickener;
And a composition containing titanium dioxide that generates a photocatalytic action by light irradiation, a compound that generates hydrogen peroxide in an aqueous solution, a thickener, phosphoric acid, and a condensed phosphate.

Moreover, in addition to the above oxidizing compounds that are tooth bleaching agents, the composition of the present invention can use acidic organic compounds or salts thereof as the tooth bleaching activator. More specifically,
(I) Formulas (a) and (b) below:

Wherein R is a linear or branched alkyl group having 2 to 19 carbon atoms, M is an alkali metal ion, alkaline earth metal ion or hydrogen ion, n is 1 or 2, And n = 1 when M is an alkali metal ion or hydrogen ion, and n = 2 when M is an alkaline earth metal ion). Is preferred.
Moreover, as an acidic organic compound of the said component (i) or its salt, following formula (c):

(Wherein m represents an integer of 7 to 13 carbon atoms) and the following formula (d):

(Wherein k represents an integer having 7 to 13 carbon atoms) is preferred.

  Examples of the compound represented by the formula (a) of the component (i) include sodium propanoyloxybenzenesulfonate, sodium butanoyloxybenzenesulfonate, sodium pentanoyloxybenzenesulfonate, sodium hexanoyloxybenzenesulfonate, Sodium heptanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, tri Sodium decanoyloxybenzenesulfonate, sodium tetradecanoyloxybenzenesulfonate, pentadecanoyloxybenzene Sodium sulfonic acid, sodium hexadecanoyloxy benzenesulfonic acid, sodium hepta decanoyl oxybenzene sulfonate, sodium octadecanoyloxy benzenesulfonic acid, and the like as the potassium salts. Among them, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, sodium undecanoyloxybenzenesulfonate, sodium dodecanoyloxybenzenesulfonate, tridecanoyloxybenzene Sodium sulfonate, sodium tetradecanoyloxybenzenesulfonate, and potassium salts thereof are preferred. In particular, sodium octanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate, and sodium dodecanoyloxybenzenesulfonate are particularly preferable.

  Examples of the compound represented by formula (b) of the component (i) include propanoyloxybenzoic acid, butanoyloxybenzoic acid, pentanoyloxybenzoic acid, hexanoyloxybenzoic acid, heptanoyloxybenzoic acid, octanoyl. Oxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, tridecanoyloxybenzoic acid, tetradecanoyloxybenzoic acid, pentadecanoyloxybenzoic acid, hexadecana Examples include noyloxybenzoic acid, heptadecanoyloxybenzoic acid, octadecanoyloxybenzoic acid, and sodium and potassium salts thereof. Among them, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, undecanoyloxybenzoic acid, dodecanoyloxybenzoic acid, and tridecanoyloxybenzoic acid are preferable. In particular, octanoyloxybenzoic acid, nonanoyloxybenzoic acid, decanoyloxybenzoic acid, and dodecanoyloxybenzoic acid are particularly preferable.

  Basically, it is important to have the basic skeleton shown in the formulas (a) and (b), and the effect of the invention on the aromatic ring and substituent R in the formulas (a) and (b). Can be present in a substituent that does not substantially interfere with (eg, a lower alkyl group). It is usually preferable not to exist. The arrangement on the aromatic ring is preferably para, but may be ortho or meta. Taking these into consideration, the compounds represented by formulas (a) and (b) are preferably compounds represented by formulas (c) and (d), respectively, as described above.

Component (i) is preferably contained in the tooth bleaching agent in an amount of 0.01 to 40% by weight, more preferably 0.1 to 30% by weight, and still more preferably 0.2 to 20% by weight.
As a tooth bleach using this acidic organic compound (i), in addition to component (i),
It is preferable to contain (ii) hydrogen peroxide, a compound that generates hydrogen peroxide, at least one peroxide selected from the group consisting of inorganic peroxides and organic peroxides, and (iii) water.
Examples of the manganese complex used as the bleach activator include a manganese group coordination complex or a salt thereof.

  The manganese group coordination complex used in the present invention is composed of a plurality of manganese atoms and a plurality of ligands, the manganese center is in the oxidation state IV, and the Mn (IV) center is antiferromagnetically bonded. (IV) base coordination complexes. The degree of antiferromagnetic coupling is generally expressed as an exchange coupling parameter. This parameter negatively affects the antiferromagnetic interaction (the antiferromagnetic coupling of transition metal ions is described, for example, by R.S. Drago, “Physical Methods in Chemistry”, 1977, Chapter 11, pp. 427. The oxidation state (IV) manganese is described by K. Weighardt et al. In "The Journal of the American Chemical Society", 1988, Vol. 110, pp. 7398-7411).

The manganese group coordination complex is, for example, the following formula (I):
^{_{[L n Mn m X p]}} z Y q (I)
[Wherein, Mn represents manganese in an IV-oxidized state, n and m each represent an integer of 2 to 8, X represents a coordination species or a crosslinking species, for example, H ₂ O, OH ⁻ , O ₂ ²⁻ , O ²⁻ , HO ₂ ⁻ , SH ⁻ , S ^{2 −} ,> SO, NR ₂ ⁻ , R—COO ⁻ , NR ₃ (R is H or substituted or unsubstituted alkyl or aryl) , Cl ⁻ , N ₃ ⁻ , SCN ⁻ , N ³⁻ , or a combination thereof, p is an integer of 0 to 32, preferably 3 to 6, and Y is a property based on the charge z of the complex And z is a positive or negative integer indicating the charge of the complex, and when z is positive, Y is an anion such as Cl ⁻ , Br ⁻ , I ⁻ , NO ₃ ⁻ , ClO ₄ ⁻ , NCS. _{^{-, PF 6 -, RSO 3}} -, RSO 4 -, CF _{^{SO 3 -, BPh 4 -,}} OAc - , and, if z is negative, Y is usually cation such represents an alkali metal, alkaline earth metal or (alkyl) ammonium, q is z / [charge of Y] L represents a plurality of heteroatoms (for example, N, P, O and S, etc.), one or antiferromagnetically coupled through all or some of the heteroatoms and / or carbon atoms And a plurality of Xs may be the same or different in structure, and they may be different from each other, such as Ls and Ys. The same applies to
Indicated by The degree of antiferromagnetic coupling | J | is preferably greater than 200 cm ⁻¹ , more preferably greater than 400 cm ⁻¹ . In the present invention, a precursor of the manganese group coordination complex can be used instead of or together with the manganese group coordination complex. Such a precursor is a component that can be easily mutated to the manganese group coordination complex, for example, a compound capable of supplying hydrogen peroxide in an aqueous solution or in an environment such as saliva, and other components, depending on circumstances. By contacting and reacting with a tooth or a component in the oral cavity, the manganese-based coordination complex of the formula (I) can be converted into the manganese-based coordination complex of the above formula (I) in a short time that the present invention can be carried out under normal temperature and normal pressure conditions. It may be a compound containing manganese that can be converted. The precursor molecule does not necessarily contain manganese in the oxidation state IV, and the manganese center does not necessarily have to be antiferromagnetically bonded. A preferable manganese group coordination complex is a manganese complex in which m = 2, n = 2, and p = 3 and the manganese (IV) center is antiferromagnetically bonded.
These are of formula (I ′):

[In the formula, each X individually represents any of the bridging species described as a coordination ion in the formula (I), and L, Y, q, and z are as defined above]
It is a dinuclear manganese (IV) -complex compound having Suitable bridging species or coordination ions are usually small molecules with donor atoms and preferably small.
More preferred manganese group coordination complexes are of the formula (I ″):
[LMn ^IV (μ-O) ₃ Mn ^IV L] ^z Y _q (I ″)
[Wherein L, Y, q and z are as defined above], and X = 0 ^2- dinuclear manganese (IV) -complex.

Ligand L is an organic molecule having a plurality of heteroatoms (eg N, P, O and S, etc.) and coordinated to the Mn (IV) center through all or some of the heteroatoms and / or carbon atoms. is there. Preferred ligands L are multidentate ligands that coordinate to an antiferromagnetically bonded manganese (IV) center through three heteroatoms, preferably each one of the manganese (IV) centers through three nitrogen atoms. Is a multidentate ligand that coordinates to The nitrogen atom may be part of a tertiary amine group, secondary amine group or primary amine group, or part of an aromatic ring system such as pyridine, pyrazole, or a combination thereof. However, the coordinating ligand to one of Mn (IV) center via three nitrogen atoms not necessarily to form the _{^{[LMn IV (μ-O)}} 3 Mn IV L] z Y q complex. Certain ligands form complexes containing other than two manganese (IV) centers. Only ligands with specific space-filling properties form effective dinuclear Mn (IV) -complexes. This means that the space filling property of the ligand L is also important in the definition of a more preferable manganese group coordination complex [LMn ^IV (μ-O) ₃ Mn ^IV L]. The space filling property of the ligand can be known by a known method such as a molecular model and / or molecular drawing. For example, ligands that produce L ₂ Mn mononuclear compounds are not very suitable (because they have insufficient space filling properties, ie these ligands are too small), and ligands that produce LMnX ₃ mononuclear compounds (excess space filling properties, That is, these ligands are too large) and are not very suitable. Other less suitable ligands are those that produce a tetranuclear L ₄ Mn ₄ O ₆ cluster, even if it is a tri-N-dentate ligand (because the space filling properties are not fully satisfactory and the cluster is Because it is a little too small). Ultimately, ligands with effective space filling properties that form LMn ^IV (μ-O) ₃ Mn ^IV L clusters are most preferred. Accordingly, the most preferred manganese group coordination complex is that in formula (I ″), the manganese IV center is antiferromagnetically bonded, L contains three or more nitrogen atoms, and the three nitrogen atoms are Mn (IV) centers. Binuclear manganese (IV) -complexes coordinated to each one. A representative of this manganese group coordination complex is represented by the formula (I ′ ″):
[(L′ N ₃ ) Mn ^IV (μ-O) ₃ Mn ^IV (N ₃ L ′)] ^z Y _q (I ′ ″)
In the formula, L′ N ₃ (and N ₃ L ′) represents a ligand containing three or more nitrogen atoms. Y may be any counter ion as defined above, but a more preferred counter ion Y is an ion that forms a solid that is hygroscopically stable. This means that the lattice filling properties of the ions are compatible with the lattice filling properties of manganese clusters. More preferred combinations of manganese clusters and counterions Y are usually larger counterions such as ClO ₄ ⁻ , PF ₆ ⁻ , RSO ₃ ⁻ , RSO ₄ ⁻ , BPh ₄ ⁻ , OOCR ⁻ (where R is substituted or unsubstituted Alkyl, aryl, etc.). Some examples of suitable ligands L are shown in their simplest form: (i) 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4 , 7-triazacyclodecane, 1,4,8-trimethyl-1,4,8-triazacycloundecane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (ii) Tris (Pyridin-2-yl) methane, tris (pyrazol-1-yl) methane, tris (imidazol-2-yl) methane, tris (triazol-1-yl) methane, (iii) tris (pyridin-2-yl) Borate, tris (triazol-1-yl) borate, tris (pyrazol-1-yl) borate, tris (imidazol-2-yl) phosphine, tris (imidazol-2-yl) borate (Iv) 1,3,5-trisamino-cyclohexane, 1,1,1-tris (methylamino) ethane, (v) bis (pyridin-2-yl-methyl) amine, bis (pyrazole-1) -Yl-methyl) amine, bis (triazol-1-yl-methyl) amine, bis (imidazol-2-yl-methyl) amine.
All of these ligands may be optionally substituted on the nitrogen atom of the amine and / or the carbon atom of CH ₂ and / or the aromatic ring.
Examples of preferred ligands are:

[Wherein, R is an alkyl group of _C 1 -C _4] or,

Wherein each R is H, substituted or unsubstituted alkyl or aryl.
Examples of the most preferred manganese group coordination complexes are:

(R is a substituent containing at least a hydrogen atom and containing 0 or more carbon atoms, and a plurality of Rs may have the same structure or different structures. R is preferably hydrogen. An atom or a methyl group.)
And more specifically, R = H or CH ₃ .

It is. The value of antiferromagnetic coupling J of these catalysts is ˜−780 cm ⁻¹ .
Examples of precursors for manganese-based coordination complexes are:

It is. Both precursors are converted in the presence of a compound capable of supplying hydrogen peroxide in aqueous solution to form the following active cation (5):

All of these complexes, regardless of whether they are preformed or formed in situ during the bleaching process, are capable of bleaching activation of peroxy compounds against many types of soils at lower temperatures using the conventionally known manganese-based and It is a catalyst that performs much more effectively than any cobalt-based catalyst. Furthermore, these catalysts have a high stability against hydrolysis and oxidation. Catalytic activity is determined by only _{[L n Mn m X p]} z core complex, the presence of _{Y q} It is noted that there is little effect on the catalytic activity. Some of the complexes described in the present invention have been prepared so far for chemical and experimental exploration, for example as models of natural manganese-protein complexes, but their practical application has been considered (K. Wieghardt et al., Journal of American Chemical Society, 1988, 110, pp. 7398 and references cited therein, as well as K. Wiegharddt et al., Journal of the Chemical Society. 1145).

The effective amount of the Mn group coordination complex is preferably 0.00001 to 0.1% by weight with respect to the composition in terms of manganese content. If the value is below the lower limit of the numerical range, the bleaching effect is lowered, which is not preferable.
The effective amount of the Mn group coordination complex is preferably 0.00001 to 0.1% by weight, more preferably 0.0002 to 0.01% by weight in terms of manganese content, and is used for tooth bleaching. It is what
Light irradiation is not necessarily required, but light irradiation may be performed.

In addition, the composition of the present invention contains at least one inorganic clay mineral selected from the group consisting of, for example, saponite, montmorillonite, stevensite, heratlite, smectite, nectite, and sepiolite as an inorganic thickener, if necessary. You can also
In addition, a pH adjuster to further increase the activity and bleaching effect of peroxides, a thickener to enhance applicability to tooth surfaces, a colorant to clarify the application range, and the storage stability of the above compounds A stabilizer for improving the viscosity can be contained.
A water-miscible solvent can be added to the above composition so that all the components can be rapidly mixed. Specific examples of the solvent include ethyl alcohol, acetone, glycerin, ethylene glycol, and propylene glycol. Among them, ethyl alcohol, acetone and glycerin are preferable, and ethyl alcohol is particularly preferable.

  In addition, the manganese group coordination complex and / or its precursor is stored separately from at least one of the other components, and it is also preferable that the manganese group coordination complex is used as a mixture during use. In the composition of the present invention, when the compound capable of supplying hydrogen peroxide in an aqueous solution and the Mn complex, which is a bleach activator, coexist in a solution state for a long period of time, the reaction proceeds, and when used, Since there is a possibility of deactivation, it is preferable to store the Mn complex separately from the composition of the present invention containing a compound that supplies hydrogen peroxide in an aqueous solution.

The second aspect of the present invention provides a tooth bleached with a tooth bleaching agent containing at least one compound selected from the group consisting of an organic peroxide, a compound that generates hydrogen peroxide in an aqueous solution, and titanium dioxide. An adhesive tooth surface pretreatment material composition containing a reducing compound for recovering the adhesive strength of the surface, wherein the reducing compound is an ascorbic acid compound. It is a surface pretreatment material composition.
Examples of the ascorbic oxygen compound used as the reducing compound include ascorbic acid metal salts such as ascorbic acid and sodium ascorbate.

  The organic peroxide used as the tooth bleaching agent and / or bleach activator, the compound that generates hydrogen peroxide in an aqueous solution, and titanium dioxide may be used in the same manner as in the first invention. I can do it. Further, for other components and matters not specifically described herein, unless otherwise specified, the same components and items as those described in the first aspect of the present invention are applied as they are or with modifications obvious to those skilled in the art. Should be understood.

  The following aspects can be commonly applied to the first and second aspects of the present invention.

First, the reducing compound is usually used as an aqueous solution. When the reducing compound is used as an aqueous solution, the concentration of the aqueous solution is not particularly limited, but is preferably 1 to 20% by weight, more preferably 2 to 20% by weight. The processing time is not particularly limited, but is preferably 1 to 600 seconds, more preferably 10 to 120 seconds. In the aqueous solution of the reducing compound, in addition to water, a water-soluble solvent such as acetone or ethanol can be mixed and used. Although there is no restriction | limiting in particular in the usage-amount of these water-soluble solvents, Usually, it is 1 to 50 weight% with respect to water.
In the present invention, an etching material may be used.

Examples of the compound suitably used as an etching material include ethylenediaminetetraacetic acid metal salt, phosphoric acid, citric acid and the like, and these compounds are used by dissolving or dispersing in an aqueous medium. These compounds can be used alone or in combination.
When the etching material is used as an aqueous solution, the concentration of the etching component in the aqueous solution is not particularly limited. For example, when an ethylenediaminetetraacetic acid metal salt is used as the etching material, preferably 5 to 50% by weight, more Preferably, it is 10 to 30% by weight. When phosphoric acid is used, it is preferably 5 to 60% by weight, more preferably 10 to 40% by weight phosphoric acid and 0.1 to 10% by weight iron phosphate. An aqueous solution containing 5 to 20% by weight of citric acid and 1 to 10% by weight of ferric chloride is preferably used. In particular, in the present invention, it is preferable to use a so-called 10-3 etching solution comprising an aqueous solution of 10 wt% citric acid and 3 wt% ferric chloride as the etching material.

In the present invention, the etching material can be used as an aqueous medium solution as described above. In this case, examples of the water-soluble solvent used with water include water-soluble solvents such as acetone and ethanol. it can. Although there is no restriction | limiting in particular in the usage-amount of these water-soluble media, Usually, it is 1 to 50 weight% with respect to water.
In the present invention, the above-described aqueous solution of the reducing compound, the aqueous solution of the etching material, and the aqueous solution of the oxidizing compound include polymers such as polyvinyl pyrrolidone, carboxymethyl cellulose, and polyvinyl alcohol as necessary to adjust the viscosity. A viscosity modifier such as a compound or highly dispersed silica can be blended. The oxidizing compound used in the present invention can be used in the form of a gel by blending them. Furthermore, this oxidizing compound can also be used with a colorant. The concentration of these viscosity modifiers and colorants is not particularly limited, but is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight.

In the present invention, a primer may be used. The primer is used on the treated tooth surface after bleaching and before placing (adhering) the cured product on the tooth. That is, the primer can be used either before or after treatment with an aqueous solution containing a reducing compound or before or after treatment with a tooth surface treatment agent. Further, this primer may be used a plurality of times.
The primer that can be used in the present invention is not particularly limited. For example, a monomer having a polymerizable organic acid or an acidic group, and a component that modifies decalcified tooth and promotes diffusion of the adhesive into the tooth. An aqueous solution containing Examples of the “component that modifies the tooth and promotes diffusion of the adhesive into the tooth” include, for example, (poly) alkylene glycol, 2-hydroxyethyl (meth) acrylate, or 1,3-dihydroxypropyl. Examples thereof include a monomer having a hydroxyl group such as mono (meth) acrylate and polyethylene glycol (meth) acrylate.

  Although there is no restriction | limiting in particular in the adhesive agent which can be used in this invention, For example, it consists of a polymerization initiator and a polymerizable monomer. Examples of the polymerization initiator include organic peroxides, inorganic peroxides, alkylboranes, partial oxides of alkylboranes, α-diketone compounds, organic amine compounds, organic sulfinic acids, organic sulfinates, inorganic sulfur compounds. And barbituric acids. These can be used alone or in combination of two or more.

  Examples of the polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylol. Aliphatic esters of (meth) acrylic acid such as propane tri (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) Polypropylene such as acrylate, nonaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylates such as tetradecaethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate Mono (meth) acrylates in which (meth) acryloyl group of one of recalled di (meth) acrylates, polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylates is substituted with methyl group or ethyl group ; Having urethane linkage such as 2- (meth) acryloyloxyethyl isocyanate or 2,2,4-trimethylhexamethylene diisocyanate or 1,3,5-trimethylhexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate adduct (Meth) acrylates; 2,2-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane obtained by further condensing (meth) acrylic acid to a product obtained by adding oxyethylene to bisphenol A ; Styrene, 4-methylstyrene, 4-chloromethylstyrene, styrene derivatives such as divinyl benzene, vinyl acetate, and the like. These polymerizable monomers can be used alone or in combination.

  As polymerizable monomers that can be used in the same manner, there are polymerizable monomers containing an acidic group in the molecule. Examples of the polymerizable group include radically polymerizable unsaturated groups having, for example, a (meth) acryloyl group, a styryl group, a vinyl group, and an allyl group. The polymerizable monomer should just contain at least 1 group selected from said polymeric group in 1 molecule.

  After bleaching, an aqueous solution containing a reducing compound is usually applied to the tooth surface in an amount of 1 μl / mm 2 to 50 μl / mm 2. After applying for 4 to 300 seconds, the coating is dried by air blow or the like. At this time, washing with water may not be performed. An etching material is applied to a tooth portion treated with an aqueous solution containing a reducing compound, and after 5 to 60 seconds, the tooth surface may be washed with water and dried. The etching material may be treated on the tooth surface before the pretreatment material is applied.

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

Example 1
After polishing human extracted teeth stored in physiological saline using # 600 water-resistant abrasive paper under running water to obtain a dentin-coated surface with a diameter of 3 mm or more, bleach Hi-Lite (Matsukaze Co., Ltd.) Manufactured according to the instruction manual and applied to the surface of the dentin and irradiated with light. After removing the bleaching agent with water, the bleaching agent was applied again and this was repeated three times.
A double-sided tape with a hole having a diameter of 3 mm was affixed to the bleached surface, and this flat surface was treated for 5 seconds with 20 μl of a 3% by weight aqueous sodium p-toluenesulfinate solution. After the treatment, it was dried by air blow. Next, 0.3 g of an etching material (green, product of Sun Medical Co., Ltd.) was applied to the treated surface, allowed to stand for 30 seconds, sufficiently washed with water, and dried by air blow.

Here, methyl methacrylate (MMA) containing 5% by weight of 4-methacryloyloxyethyl trimellitic anhydride (4-META), tributyl boron partial oxide (TBB-O / manufactured by Sun Medical Co., Ltd.) and poly A SUS rod was planted with a curable composition in which methyl methacrylate powder (PMMA / Sun Medical Co., Ltd.) was mixed at a weight ratio of 10/1/10 and allowed to stand for 15 minutes to cure, and then 24 hours. It left still in 37 degreeC water.
Then, it used for the adhesion test. The adhesion test was a tensile test at a crosshead speed of 2 mm / min. The measurement results are shown in Table 1.

Example 2
After the human extracted teeth stored in physiological saline are polished, the bleaching agent Hi-Lite (manufactured by Matsukaze Co., Ltd.) is applied to the surface of the enamel according to the instruction manual and irradiated with light. went. After removing the bleaching agent with water, the bleaching agent was applied again and this was repeated three times.
A double-sided tape with a hole having a diameter of 3 mm was affixed to the bleached surface, and this flat surface was treated for 5 seconds with 20 μl of a 3% by weight aqueous sodium p-toluenesulfinate solution. After the treatment, it was dried by air blow.

30 g of 4-META, 30 g of MMA, 30 g of 2.6E (condensation of 1 mol of bisphenol A ethylene oxide adduct and 2 mol of methacrylic acid (number of added chains of ethylene oxide m + n ≧ 2.6)), 0 .1 g of d, l-camphorquinone (CQ), 30 g of acetone and 10 g of distilled water were mixed and dissolved. This liquid is put into a dripping type bottle (bottle 1), 2 drops (0.05 g) of the solution and one cata sponge (manufactured by Sun Medical Co., Ltd.) are vigorously stirred for 5 seconds in a dappen dish, and the sponge is used as it is. A large amount (approx. 0.015 g) was applied to the defined area of the tooth and allowed to stand for 30 seconds. Excess liquid was blown off while lightly air blowing, and then cured by irradiating with a visible light irradiator (Translux CL, Kulzer) for 20 seconds. Place a 1mm thick cardboard with a 3.0mm inner diameter circular hole with an adhesive on one side so that the specified surface can be seen, and then fill this hole with a composite resin (Metafil C, Sun Medical Co., Ltd.) And covered with a polyester film having a thickness of 50 μm. After irradiating light on the film with a visible light irradiator (Translux CL, Kulzer) for 40 seconds to cure the composite resin, the film is peeled off and a SUS stick is placed with Sparbond C & B (Sun Medical Co., Ltd.). Planted and allowed to stand for 15 minutes. After being immersed in 37 ° C. water for one day, a tensile test was performed at a crosshead speed of 2 mm / min.
The measurement results are shown in Table 1.

Example 3
After the human extracted teeth stored in physiological saline are polished before bleaching, a bleaching agent, White White Excel (Discus Dental, Inc.) is applied to the enamel surface according to the instruction manual, 2 hours Thereafter, the bleach was removed by washing with water. This operation was performed for 14 days.
A double-sided tape with a hole having a diameter of 3 mm was affixed to the bleached surface, and this flat surface was treated for 5 seconds with 20 μl of a 3% by weight aqueous sodium p-toluenesulfinate solution. After the treatment, it was dried by air blow.

30 g of 4-META, 30 g of MMA, 30 g of 2.6E (condensation of 1 mol of bisphenol A ethylene oxide adduct and 2 mol of methacrylic acid (number of added chains of ethylene oxide m + n ≧ 2.6)), 0 .1 g of d, l-camphorquinone (CQ), 30 g of acetone and 10 g of distilled water were mixed and dissolved. This liquid is put into a dripping type bottle (bottle 1), 2 drops (0.05 g) of the solution and one cata sponge (manufactured by Sun Medical Co., Ltd.) are vigorously stirred for 5 seconds in a dappen dish, and the sponge is used as it is. A large amount (approx. 0.015 g) was applied to the defined area of the tooth and allowed to stand for 30 seconds. Excess liquid was blown off while lightly air blowing, and then cured by irradiating with a visible light irradiator (Translux CL, Kulzer) for 20 seconds. Place a 1mm thick cardboard with a 3.0mm inner diameter circular hole with an adhesive on one side so that the specified surface can be seen, and then fill this hole with a composite resin (Metafil C, Sun Medical Co., Ltd.) And covered with a polyester film having a thickness of 50 μm. After irradiating light on the film with a visible light irradiator (Translux CL, Kulzer) for 40 seconds to cure the composite resin, the film is peeled off and a SUS stick is placed with Sparbond C & B (Sun Medical Co., Ltd.). Planted and allowed to stand for 15 minutes. After being immersed in 37 ° C. water for one day, a tensile test was performed at a crosshead speed of 2 mm / min.
The measurement results are shown in Table 1.

Comparative Example 1
In Example 1, it bonded without performing the process by sodium p-toluenesulfinate aqueous solution, and used for the adhesion test after that. The adhesion test was a tensile test at a crosshead speed of 2 mm / min. Table 1 shows the measurement results.

Comparative Example 2
In Example 2, it adhered without performing the process by sodium p-toluenesulfinate aqueous solution, and used for the adhesion test after that. The adhesion test was a tensile test at a crosshead speed of 2 mm / min. The measurement results are shown in Table 1.

Comparative Example 3
In Example 3, it adhered without performing the process by sodium p-toluenesulfinate aqueous solution, and used for the adhesion test after that. The adhesion test was a tensile test at a crosshead speed of 2 mm / min. Table 1 shows the measurement results.

Claims (14)

In order to restore the adhesive force of a tooth surface bleached with a tooth bleaching agent containing at least one compound selected from the group consisting of organic peroxides, compounds that generate hydrogen peroxide in an aqueous solution and titanium dioxide An adhesive tooth surface pretreatment material composition comprising a reducing compound, wherein the reducing compound is at least one compound selected from the group consisting of sulfinic acids, inorganic sulfites, amine compounds, and ammine complex salts. A tooth surface pretreatment material composition for adhesion after bleaching, comprising: Restoring the adhesion of tooth surfaces treated with a tooth bleaching agent containing at least one compound selected from the group consisting of organic peroxides, compounds that generate hydrogen peroxide in aqueous solutions and titanium dioxide An adhesive tooth surface pretreatment material composition containing a reducing compound for bleaching, wherein the reducing compound is an ascorbic acid compound. The tooth surface pretreatment material composition according to claim 1 or 2, wherein the tooth bleaching agent contains titanium dioxide and a compound that generates hydrogen peroxide in an aqueous solution. The tooth surface pretreatment material composition according to claim 1, wherein the tooth bleaching agent further contains a bleach activator selected from the group consisting of an acidic organic compound, a salt thereof and a manganese complex. The acidic organic compound and its salt are represented by the following formulas (a) and (b):

(In the formula, R represents a linear or branched alkyl group having 2 to 19 carbon atoms, M represents an alkali metal ion, an alkaline earth metal ion or a hydrogen ion, n is 1 or 2, and M is an alkali. And n = 1 when M is a metal ion or a hydrogen ion, and n = 2 when M is an alkaline earth metal ion). 4. The tooth surface pretreatment material composition according to 4. The salt of the acidic organic compound is represented by the following formula (c):

The tooth surface pretreatment material composition according to claim 4, wherein m represents an integer of 7 to 13 carbon atoms. The acidic organic compound is represented by the following formula (d):

The tooth surface pretreatment material composition according to claim 4, wherein k represents an integer of 7 to 13 carbon atoms. The tooth bleach is (i) an acidic organic compound,
(Ii) at least one peroxide selected from the group consisting of a compound that generates hydrogen peroxide in an aqueous hydrogen peroxide solution, an inorganic peroxide, and an organic peroxide;
(iii) The tooth surface pretreatment material composition according to any one of claims 4 to 8, comprising water. The compound that generates hydrogen peroxide in an aqueous solution is at least one selected from the group consisting of perborate, percarbonate, persulfate, perphosphate, calcium peroxide, magnesium peroxide, and urea peroxide. The tooth surface pretreatment material composition according to claim 1, which is a peroxide. The tooth surface pretreatment material composition according to claim 1 or 2, wherein the tooth bleaching agent contains a manganese complex and a compound that generates hydrogen peroxide in an aqueous solution. The tooth surface pretreatment material composition according to claim 1 or 2, wherein the tooth bleaching agent further contains a thickener. The tooth surface pretreatment material composition according to claim 1 or 2, wherein the tooth bleaching agent further contains phosphoric acid and a condensed phosphate. The tooth surface pretreatment material composition according to claim 1, wherein the reducing compound is at least one compound selected from the group consisting of sodium thiosulfate, sodium p-toluenesulfinate, and an ammine complex salt. A kit comprising the tooth bleaching agent according to claim 1 or 2 and a tooth surface pretreatment material composition for adhesion after tooth bleaching.