JP2013112672A - Dental adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental adhesive composition containing an acid group-containing polymerizable monomer which can improve its storage stability while retaining its adhesiveness and in which the acid group-containing polymerizable monomer can be effectively suppressed of hydrolysis even in the existence of water.SOLUTION: The dental adhesive composition including a polymerizable monomer component (A) containing the acid group-containing polymerizable monomer, water (B), and a water-soluble organic solvent (C) is characterized in that the composition further includes trehalose (D).

Description

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

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

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

The etching process is a process of demineralizing the tooth using an acid aqueous solution, and the dentin made of rough enamel or sponge-like collagen fibers is exposed on the surface of the tooth demineralized by the acid. Become. After the etching process, the adhesion mechanism of the adhesive to the exposed enamel and dentin is different, and is specifically as follows.
Adhesion of the adhesive to the enamel is achieved by a macro mechanical fit in which the adhesive component penetrates and cures to the rough surface deashed with the acid aqueous solution. On the other hand, adhesion of the adhesive to the dentin is achieved by a micro mechanical fitting in which the adhesive component penetrates into the fine voids of the sponge-like collagen fibers exposed after decalcification and hardens. . However, the adhesive component is not easy to penetrate into the fine voids of the collagen fibers, and after the decalcification treatment, after further priming treatment (penetration) with a primer (penetration accelerator), the adhesive is applied. is necessary.

  As described above, in order to obtain good adhesion strength to both enamel and dentin, it is necessary to perform two-stage pretreatments of etching and priming when restoring damaged teeth. In addition, a three-step system in which the two-stage pretreatment is performed and an adhesive is applied and cured is employed, and there is a problem that the operation is complicated.

  Thereafter, simplification of the operability of the dental adhesive was required, and a one-component pretreatment material having both a decalcification function and a penetration promotion function has become mainstream. That is, by simplifying the two-stage pretreatment of the etching process and the priming process into one stage, the tooth restoration operation is applied and hardened by applying the adhesive after the one-stage pretreatment from the conventional three-step system. It became a two-step system, and operability was greatly improved (Patent Documents 1 and 2).

  Furthermore, in recent years, one-component adhesives have been developed, and adhesive compositions having both a deashing function and a penetration promoting function have become mainstream without requiring pretreatment such as etching and priming. Yes. Accordingly, the operability of the conventional two-step system is greatly simplified from that of the one-step system.

For example, Patent Document 3 discloses a one-component dental adhesive made of a polymerizable monomer containing a polymerizable monomer having an acidic group and requiring no pretreatment.
That is, by introducing an acidic group into the polymerizable monomer, the adhesive solution can be made acidic, so that it is not necessary to prepare an aqueous acid solution separately, and the deashing function is achieved by the acidity of the adhesive. became. Further, by blending a hydrophilic monomer and a hydrophobic monomer into the adhesive material, an effect of promoting penetration into dentin can be achieved, and it is not necessary to separately perform a priming treatment.

  However, although these one-part adhesives have achieved the purpose of simplifying operability, they require water when performing the etching process, so the acidic group-containing polymerizable monomer having a deashing function is It is necessary to coexist with water, and as a result, there is a problem that hydrolysis of the acidic group-containing polymerizable monomer occurs. That is, an adhesive material in which the acidic group is removed from the polymerizable monomer by hydrolysis, and the acidic group-containing polymerizable monomer, which is an active ingredient of the adhesive material, is decomposed, resulting in a decrease in adhesion to the tooth. Deterioration of itself (storage stability) is a problem.

  Under such circumstances, there has been a strong demand for a technique for suppressing the hydrolysis of an acidic group-containing adhesive monomer in the presence of water and improving storage stability in a one-component adhesive.

JP2003-073218 JP 2001-026511 A JP2007-119404A

  Accordingly, an object of the present invention is to provide a dental adhesive composition containing an acidic group-containing polymerizable monomer, while maintaining its adhesive strength and improving storage stability, even in the presence of water, An object of the present invention is to provide a dental adhesive composition that can effectively suppress hydrolysis of an acidic group-containing polymerizable monomer.

  As a result of researches to solve the above problems, the present inventors effectively suppress hydrolysis of acidic group-containing polymerizable monomers in an adhesive composition by water by adding trehalose. As a result, the present invention has been completed.

According to the present invention,
(A) a polymerizable monomer component containing an acidic group-containing polymerizable monomer (A1);
(B) water; and (C) a water-soluble organic solvent;
In a dental adhesive composition comprising
The composition further comprises:
(D) trehalose;
The dental adhesive composition characterized by containing is provided.

In the dental adhesive composition of the present invention,
(1) The amount of trehalose (D) is 1 to 100 parts by mass per 100 parts by mass of the acidic group-containing polymerizable monomer (A1).
(2) The polymerizable monomer component (A) contains 5% by mass or more of an acidic group-containing polymerizable monomer,
(3) The acidic group of the acidic group-containing polymerizable monomer is a phosphoric acid group,
(4) Furthermore, it contains a polymerization initiator (E),
Is preferred.

The dental adhesive composition of the present invention dramatically suppresses hydrolysis of the acidic group-containing polymerizable monomer by blending trehalose with the adhesive composition containing the acidic group-containing polymerizable monomer. It is also excellent in storage stability, and exhibits high and stable adhesion to the tooth.
The reason for the hydrolysis-preventing effect due to the addition of trehalose has not yet been elucidated, but the present inventors believe that the affinity of trehalose for water may be a factor for preventing hydrolysis. That is, trehalose molecules having high affinity for water form large molecular aggregates due to strong interaction with water molecules, and these aggregates serve as a barrier to effectively hydrolyze acidic group-containing polymerizable monomers. I think it can be prevented. In addition, since many water molecules form aggregates with trehalose, the amount of free water molecules is relatively small, which is considered to be a factor that effectively suppresses hydrolysis.

  Furthermore, the adhesive composition of the present invention containing trehalose has an excellent effect on both the deashing function and the penetration promoting function because the acidic group-containing polymerizable monomer is stably present without hydrolysis. It has a high adhesive strength for both enamel and dentin. Therefore, the adhesive composition of the present invention does not require a two-step pretreatment of etching treatment and priming treatment when adhering to a tooth, and a composite resin and a tooth substance (enamel and dentin) by a one-step operation. A highly reliable adhesive force can be obtained on both sides.

  The dental adhesive composition of the present invention exhibits acidity, and is a polymerizable monomer component (A) containing an acidic group-containing polymerizable monomer (A1), water (B), and a water-soluble organic solvent. (C), and further obtained by blending trehalose (D). This composition is used as a primer (pretreatment agent for a tooth) or an adhesive when bonding the composite resin and the tooth. In particular, when using the adhesive composition as an adhesive, it is necessary to add a polymerization initiator (E).

<(A) Polymerizable monomer component>
In the present invention, a polymerizable monomer component (hereinafter simply referred to as “monomer component”) (A) is used for curing by polymerization and imparting adhesiveness to a composite resin, various prosthetics, and the like. However, it is necessary to contain the acidic group-containing polymerizable monomer (A1) in order to provide a decalcification function for the tooth.

  The acidic group-containing polymerizable monomer (hereinafter sometimes referred to simply as “acidic group-containing monomer”) (A1) includes at least one polymerizable unsaturated group and at least one acidic group in one molecule. If it is a polymerizable monomer which has a group, it will not restrict | limit, A well-known thing can be used.

  Examples of the polymerizable unsaturated group include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. In particular, an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group are preferable from the viewpoint of curing speed, and an acryloyl group and a methacryloyl group are most preferable.

  The acidic group-containing monomer (A1) is a compound having an acidic group derived from an acid in the molecule together with a polymerizable unsaturated group. As the acidic group, a phosphoric acid group, a carboxylic acid group and the like can be used, and among them, the phosphoric acid group is most preferable. The polymerizable monomer containing a phosphoric acid group not only has a high decalcifying action on teeth, but also has a high adhesive strength on composite resins and teeth.

但し、上記化合物中、Ｒ^１は水素原子またはメチル基を表す。
上述した酸性基含有単量体(Ａ１)は、１種単独で使用されていてもよいし、２種以上を併用することもできる。 The following compounds can be illustrated as a specific example of the polymerizable monomer containing such a phosphate group.

However, in the above compounds, R ¹ represents a hydrogen atom or a methyl group.
The acidic group-containing monomer (A1) described above may be used alone or in combination of two or more.

In addition, as what is used suitably by said acidic group containing monomer (A1), the monomer which has the following phosphinic acid groups, phosphonic acid groups, and phosphonic acid hydrogen ester groups can be illustrated.
A polymerizable monomer having a phosphinic acid group;
Bis (2-methacryloxy) phosphonic acid Bis (methacryloxypropyl) phosphinic acid Bis (methacryloxybutyl) phosphinic acid polymerizable monomer having phosphonic acid group;
3-methacryloxypropylphosphonic acid 2-methacryloxyethoxycarbonylmethylphosphonic acid 4-methacryloxybutoxycarbonylmethylphosphonic acid 6-methacryloxyhexyloxycarbonylmethylphosphonic acid 2- (2-ethoxycarbonylallyloxy) ethylphosphonic acid hydrogen phosphonate monoester A polymerizable monomer having a group;
2-methacryloxyethylphosphonic acid mono (methacryloxyethyl) ester 2-methacryloxyethylphosphonic acid monophenyl ester

  In the present invention, the amount of the acidic group-containing monomer (A1) used is not particularly limited. For example, the total amount of the monomer component (A) is the acidic group-containing monomer (A1). Alternatively, a part of the monomer component (A) may be the acidic group-containing monomer (A1). However, from the viewpoint of exhibiting appropriate penetrability to the tooth of the adhesive composition and improving the strength of the cured product, the polymerizable monomer (A2) having no acidic group and the acidic group-containing monomer ( A1) is preferably used in combination as the monomer component (A). In particular, from the viewpoint of improving the adhesive strength to both enamel and dentin, it is 5% by mass or more, more preferably 5 to 80% by mass, most preferably 10%, based on the total amount of the acidic group monomer component (A). It is preferable to use the acidic group-containing monomer (A1) in the range of ˜60 mass%. If the amount of the acidic group-containing monomer (A1) is small, the adhesive strength to the enamel tends to decrease, and conversely if it is large, the adhesive strength to the dentin tends to decrease.

  In the present invention, a polymerizable monomer having no acidic group (hereinafter referred to as “non-acidic monomer”) (A2) is used in combination with the acidic group-containing monomer (A1). Can do. As such a non-acidic monomer (A2), a compound having at least one polymerizable unsaturated group in the molecule and having no acidic group is used. Specific examples of such a non-acidic monomer (A2) can include the following compounds, and these can be used alone or in combination of two or more.

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

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) acryloyloxyethoxyethoxy] propane 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl]
Propane 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane 1,4-butanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate Trimethylolpropane tri (meth) acrylate Urethane (meth) acrylate Epoxy (meth) acrylate

  Further, as the non-acidic monomer (A2), at least one polymerizable monomer other than the (meth) acrylate monomer can be used in combination with the (meth) acrylate monomer. It is.

  Non-acidic monomers (A2) other than the above include fumaric acid ester compounds such as dimethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer System derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate;

  When a highly hydrophobic polymerizable monomer is used as the non-acidic monomer (A2), an amphiphilic monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is used. In order to obtain high adhesive strength, it is preferable to use a monomer together to prevent separation of water and to ensure a uniform composition.

<Water (B)>
In the present invention, in order to have the decalcification function described above, water is required together with an acidic group. This is because if water is not present, the etching process on the tooth cannot be performed well.

In the present invention, when the adhesive composition of the present invention is applied to the tooth surface, the water is preferably removed by air blow prior to the curing of the composition from the viewpoint of sufficiently proceeding with the curing. .
Since a certain amount of moisture is present in the oral cavity environment to which the dental adhesive composition of the present invention is applied, even if the adhesive composition of the present invention does not contain water, Dental adhesive composition Demineralization of the tooth by the predetermined demineralization action and good adhesion is demonstrated, but the use of water is indispensable to demineralize more sufficient tooth It is preferable that it is contained to some extent.

  In the present invention, such water (B) is preferably used in an amount of 10 to 120 parts by mass, particularly 50 to 100 parts by mass, per 100 parts by mass of the acidic group-containing monomer (A1).

<Water-soluble organic solvent (C)>
The water-soluble organic solvent (C) used in the adhesive of the present invention improves the miscibility of the monomer component (A) and water (B) with the polymerization initiator (E) used as described later. In order to obtain an adhesive having a uniform composition.

  As the water-soluble organic solvent, known organic solvents can be used without any limitation as long as they are volatile at room temperature and exhibit water-solubility. The term “volatile” as used herein means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. The term “water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 ml or more. Specific examples of such volatile water-soluble organic solvents include methanol, ethanol, propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of harmfulness to living organisms, ethanol, propanol or acetone is preferable.

  The blending amount of the water-soluble organic solvent (C) in the adhesive of the present invention may be such that each component blended as described above is uniform, and per 100 parts by mass of the acidic group-containing monomer (A1). 100 to 600 parts by mass is preferable, and 200 to 500 parts by mass is particularly preferable.

で表わされる化合物であり、接着性を有する酸性基含有単量体（Ａ１）に導入された酸性基の加水分解を抑制するために用いる成分である。 <Trehalose (D)>
Trehalose (D) used in the adhesive composition of the present invention has the following formula:

And is a component used for suppressing hydrolysis of acidic groups introduced into the acidic group-containing monomer (A1) having adhesiveness.

  The blending amount may be a level that suppresses hydrolysis of the acidic group-containing monomer (A1) in consideration of the blending amount of the acidic group-containing monomer (A1) and the blending amount of water (B). However, it is preferably blended at 1 to 100 parts by mass per 100 parts by mass of the acidic group-containing monomer (A1), more preferably 10 to 50 parts by mass per 100 parts by mass of the acidic group-containing monomer (A1). .

  Since trehalose (D) itself does not contribute to adhesiveness, if the blending amount is too large, the blending amount of the monomer component (A) decreases, and the adhesive strength may be lowered. Moreover, when there are too few compounding quantities of trehalose (D), the inhibitory effect of a hydrolysis of an acidic group containing monomer (A1) will become inadequate, and storage stability will fall, Eventually the adhesive material of adhesive composition As a function will be impaired.

  In addition, since it is an adhesive composition used in the oral cavity, it is extremely important to use trehalose from the viewpoint that a component causing caries cannot be used. The majority of saccharides become caries fungi and induce caries, but trehalose is not only a cartilage fungus, but also has the effect of suppressing caries, and is effective in preventing caries. Is also effective.

<Polymerization initiator (E)>
The adhesive composition of the present invention may contain an effective amount of a polymerization initiator (E), and when it is used as an adhesive, it is necessary to add a polymerization initiator.

  Such a polymerization initiator (E) is preferably a photopolymerization initiator because it can be polymerized and cured at an arbitrary timing. As the photopolymerization initiator, a compound that itself generates radical species by light irradiation or a mixture obtained by adding a polymerization accelerator to such a compound is used.

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

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

  The blending amount of such a polymerization initiator (E) is not particularly limited as long as it is an effective amount capable of curing the adhesive composition, and may be set as appropriate. It is good to set it as the range of 0.5-50 mass parts per 100 mass parts of bodies (A1), especially 1-20 mass parts. If it is less than 0.5 part by mass, the polymerization tends to be insufficient, and if it exceeds 20 parts by mass, the strength of the cured product tends to decrease.

<Other ingredients>
In the adhesive composition of the present invention, if the above components (A) to (D) and, if necessary, a polymerization initiator (E) component are blended, the adhesive composition has excellent adhesiveness to tooth and composite resin. Although expressed, it is preferable to add an inorganic filler in order to improve the mechanical strength and water resistance of the adhesive composition.
Examples of such inorganic fillers include borosilicate glass, soda glass, glass containing heavy metals (eg, barium, strontium, zirconium), aluminosilicate, glass ceramics, silica, silica / zirconia, silica / titania, silica / alumina, etc. A composite inorganic oxide etc. are mentioned, Among these, silica is the most preferable.

  These inorganic fillers can be improved in mechanical strength and water resistance by being hydrophobized with a surface treatment agent typified by a silane coupling agent to improve the compatibility with the polymerizable monomer. The hydrophobization method may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, etc. hexamethyldisilazane is preferably used. The various fillers can be used alone or in admixture of two or more.

  The compounding amount of the inorganic filler used in the present invention is preferably 10 to 200 parts by mass, particularly 20 to 100 parts by mass per 100 parts by mass of the acidic group-containing monomer (A1). Most preferably it is used. When the blending amount of the inorganic filler is less than 10 parts by mass, the strength and water resistance of the adhesive composition are insufficient, and when it exceeds 40 parts by mass, the curability of the adhesive composition becomes insufficient and the teeth Adhesive strength with quality decreases.

  Further, in the present invention, other components known as compounding components of the dental adhesive composition, for example, an acidic group-containing radical polymerizable monomer, as long as the adhesive composition does not impair the adhesiveness. A radical polymerizable monomer other than the polymer and the polyfunctional radical polymerizable monomer, an ultraviolet absorber, a polymerization inhibitor, a polymerization inhibitor, a dye, a pigment, and the like may be blended.

  The method for producing the adhesive composition of the present invention is not particularly limited, and may be performed in accordance with a known method for producing an adhesive composition for a tooth, generally under an inert light such as red light. All the ingredients to be blended may be weighed and mixed well until a uniform solution is obtained.

  The method of using the adhesive composition of the present invention may also follow the known method of using the adhesive composition for dental materials. When used as an adhesive, the tooth that becomes an adherend from which the carious portion has been removed, etc. After applying the adhesive composition of the present invention to the material and leaving it to stand for about 5 to 60 seconds, lightly blown compressed air or the like to volatilize the volatile components, and after filling a prosthesis such as a composite, then a dental irradiator It is only necessary to polymerize and cure by irradiating with visible light using

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited to these Examples. Abbreviations and abbreviations shown in the examples are as follows.

Polymerizable monomer component (A)
[Acid group-containing polymerizable monomer (A1)]
PM1: 2-methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate MHP: 6-methacryloyloxyhexyl dihydrogen phosphate MDP: 10-methacryloyloxydecyl dihydrogen phosphate

[Non-acidic polymerizable monomer (A2)]
Bis-GMA: 2,2′-bis [4- (2-hydroxy-3-methacryloxy)
Propoxy) phenyl] propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate

Water-soluble organic solvent (C)
IPA: isopropyl alcohol

Polymerization initiator (E)
CQ: camphorquinone DMBE: ethyl p-N, N-dimethylaminobenzoate

Other ingredients (inorganic filler)
F1: Amorphous silica having a particle size of 0.02 μm (treated with methyltrichlorosilane)
F2: spherical silica-zirconia having a particle size of 0.4 μm (γ-methacryloyloxypropyltrimethoxysilane hydrophobized product) and spherical silica having a particle size of 0.08 μm
Mixture of 70:30 by mass with titania (γ-methacryloyloxypropyltrimethoxysilane hydrophobized product)

In the following examples and comparative examples, various measurements were performed by the following methods.
(1) Measuring method of storage stability (acid group-containing monomer (A1) residual rate) 0.05 g of the dental adhesive composition immediately after adjustment was placed in 4.95 g of acetonitrile, and dissolved while stirring. A solution was obtained. 5 μl of this liquid was measured by liquid chromatography (MD-2010 Plas, JASCO Corporation), the peak area of the acidic group-containing monomer (A1) in the liquid was calculated, and the resulting peak area was determined to be acidic. The initial abundance (S1) of the group-containing monomer (A1) was used.
Next, after this adhesive was stored in an incubator at 50 ° C. for 3 weeks, the peak area of the acidic group-containing monomer (A1) in the liquid was calculated and obtained using the same method as described above. The peak area was defined as the abundance (S2) after storage of the acidic group-containing monomer (A1).
The residual ratio (%) of the acidic group-containing monomer (A1) after storage at 50 ° C. for 3 weeks was calculated by the following calculation formula.
Residual amount of acid group-containing monomer (%) = (S2 / S1) × 100%

The measurement conditions for the liquid chromatography are as follows.
Developing solvent: acetonitrile / 1.0% aqueous phosphoric acid solution = 50/50
Column: “Inertsil ODS-2” manufactured by GL Sciences Inc.
Flow rate: 1.0 ml / min
Measurement wavelength: 210 nm
Sample injection amount: 5 μl

(2) Measuring method of tooth adhesiveness (initial adhesiveness) a) Preparation method of adhesion test piece The bovine front teeth are removed within 24 hours after slaughter, and parallel with the lip surface with # 600 emery paper under running water. So that the enamel and dentin planes were cut out.
Next, after compressed air was blown onto these surfaces for about 10 seconds and dried, a double-sided tape with a hole having a diameter of 3 mm was fixed to either the enamel or dentin plane, and then the thickness was 0.5 mm. Then, a paraffin wax having a hole having a diameter of 8 mm was fixed on the circular hole so as to have the same center, thereby forming a simulated cavity.
A dental adhesive is applied to the simulated cavity, left for 20 seconds, dried by blowing compressed air for about 10 seconds, and then lighted for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Irradiated.
Furthermore, a dental composite resin (Esterite Σ, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece.
b) Adhesion test method The above-mentioned adhesion test piece was immersed in water at 37 ° C for 24 hours, and then pulled at a crosshead speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). Tensile bond strength was measured. For each test piece, the tensile bond strength was measured by the above method for four test pieces, and the average value was used as the initial bond strength for enamel or dentin to evaluate the adhesion to the tooth.

(3) Evaluation Method for Storage Stability (Adhesive Strength) The prepared dental adhesive composition was stored in a 50 ° C. incubator for 3 weeks, and then the tensile adhesive strength was measured in the same manner as described above. The tensile bond strength was measured for four test pieces per test, and the average value was defined as the bond strength after 3 weeks storage at 50 ° C. with respect to enamel or dentin.

<Example 1>
10 g of PM1 as the acidic group-containing monomer (A1), 18 g of Bis-GMA and 12 g of 3G as the non-acidic polymerizable monomer (A2), 7.6 g of water (B), water-soluble organic solvent (C ) 34 g of IPA, 2.8 g of trehalose (D) and 5 g of CQ and DMBE as polymerization initiators (E), respectively, and stirred until a uniform solution is obtained. I adjusted things.
Using this adhesive composition, with respect to enamel and dentin, initial bond strength and storage stability (residual rate and bond strength of PM1 component after storage at 50 ° C. for 3 weeks) It was measured. The composition of the adhesive composition is shown in Table 1, and the evaluation results are shown in Table 2.

<Example 2 to Example 21>
Adhesive compositions having different compositions were prepared according to the method of Example 1, and the initial adhesive strength and storage stability (residual ratio and adhesion of the A1 component after storage at 50 ° C. for 3 weeks) were applied to enamel and dentin. Strength) was measured. Each composition of the adhesive composition is shown in Table 1, and the evaluation results are shown in Table 2.

<Comparative Examples 1 to 10>
Adhesive compositions having different compositions were prepared according to the method of Example 1, and the initial adhesive strength and storage stability (residual ratio and adhesion of the A1 component after storage at 50 ° C. for 3 weeks) were applied to enamel and dentin. Strength) was measured. Each composition of the adhesive composition is shown in Table 3, and the evaluation results are shown in Table 4.

  Examples 1 to 21 were formulated so as to satisfy all the requirements of the present invention. In any case, the remaining acidic group-containing monomer (A1) after storage at 50 ° C. for 3 weeks The rate was high, the adhesive strength was maintained, and it had good storage stability.

  On the other hand, Comparative Examples 1 to 4 are cases where trehalose (D) was not blended, but in any case, the acid group-containing monomer (A1) was stored after storage at 50 ° C. for 3 weeks. Most of them were hydrolyzed, and the adhesive strength was greatly reduced.

  Comparative Examples 5 and 6 are cases where glucose and sucrose were blended instead of blending trehalose (D), respectively, but in any case, after storage at 50 ° C. for 3 weeks, an acidic group-containing monomer ( Most of A1) was hydrolyzed, and the adhesive strength was greatly reduced.

  Comparative Example 7 is the case where the acidic group-containing monomer (A1) was not blended, and Comparative Example 8 was the case where water (B) was not blended. Decalcification is not obtained, and the adhesive strength to dentin and enamel is greatly reduced.

  Comparative Example 9 is a case where the water-soluble organic solvent (C) was not blended, but the viscosity of the adhesive composition increased, the tooth decalcification and penetrability were insufficient, and the dentin and enamel The adhesive strength is greatly reduced.

  Comparative Example 10 is a case where the polymerization initiator (E) was not blended, and since polymerization and curing were not performed, adhesion to dentin and enamel was not obtained. That is, when the adhesive composition is used as an adhesive, a polymerization initiator (E) is required.

Claims (5)

(A) a polymerizable monomer component containing an acidic group-containing polymerizable monomer (A1);
(B) water; and (C) a water-soluble organic solvent;
In a dental adhesive composition comprising
The composition further comprises:
(D) trehalose;
The dental adhesive composition characterized by containing.   The dental adhesive composition according to claim 1, wherein the amount of the trehalose (D) is 1 to 100 parts by mass per 100 parts by mass of the acidic group-containing polymerizable monomer (A1).   The dental adhesive composition according to claim 1 or 2, wherein the polymerizable monomer component (A) contains 5% by mass or more of the acidic group-containing polymerizable monomer (A1).   The dental adhesive composition according to any one of claims 1 to 3, wherein the acidic group of the acidic group-containing polymerizable monomer (A1) is a phosphoric acid group.   Furthermore, the dental adhesive composition in any one of Claims 1 thru | or 4 containing the polymerization initiator (E).