JP2848974B2 - Dental adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental adhesive having excellent adhesion between a tooth material and a dental restorative material, and excellent edge sealing properties.

[0002]

BACKGROUND OF THE INVENTION In recent years, in the field of dental materials, various adhesives having excellent adhesiveness to teeth, particularly dentin, have been developed. As an adhesive component of an adhesive used in the technical field of dental materials, a polymerizable monomer having an acidic group in a molecule is used. For example, (meta)
Phosphoric acid diester groups (see Japanese Unexamined Patent Publication No.
2-113089), a phosphoric acid monoester group (Japanese Unexamined Patent Publication No.
See JP 58-21607), were introduced carboxyl group, acid anhydride group (see JP-A-54-11149) and acid halide group (see JP-A-57-151607) groups such as polymerization It is a functional monomer.

[0003] In addition to the (meth) acrylic acid-based compound having the above group, hydroxyethyl (meth) acrylate (HE) is used as an adhesive component of a general adhesive.
Adhesives using (meth) acrylates of polyhydroxy compounds, such as MA) or glyceryl mono (meth) acrylate (GM), have also been used.

[0004] However, dental restorative materials are used under severe conditions that cannot be compared with so-called general adhesive applications. Therefore, in such an application, in addition to the properties of the conventional adhesive, it is necessary that the performance such as adhesiveness, edge sealing property and hydrophilicity be well balanced.

The inventors of the present invention have found that in such dental adhesives, the number of hydroxyl groups contained in the (meth) acrylate-based polymerizable monomer depends on the adhesiveness, margin blocking property, hydrophilicity and the like. The present invention has been found to have a great influence on the performance balance.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a dental adhesive using a novel (meth) acrylate compound , which has excellent adhesiveness.
In addition to the formation of gaps between the tooth and the restorative material
The marginal sealing ability and the hydrophilicity of the adhesive
With the aim of providing dental adhesives with excellent
I have.

[0007]

[0008]

The dental adhesive of the present invention has the following formula [1]
Mesoerythritol mono (meth) acrylate represented
And / or pentaerythritol represented by the following formula [2]
Mono (meth) acrylate and the mono (meth) acrylate
At least one olefin copolymerizable with a related compound
Containing a polymerizable monomer having an inductive double bond
It is characterized by.

[0009]

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[0010] [1]

[0011]

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[2] In the formulas [1] and [2], R represents a hydrogen atom or a methyl group.

[0013] The formula [1] or mono (meth) acrylate compound represented by the formula [2] has together three hydroxy Le group in the molecule. Thus dental adhesive containing mono (meth) acrylate compound having three hydrin <br/> proxy Le group, adhesion and very good balance of properties such as marginal sealing and hydrophilic .

[0014]

DETAILED DESCRIPTION OF THE INVENTION Used in the dental adhesive of the present invention
New acrylate compounds represented by the following formula [1]
Acrylate compound mesoerythritol mono (meth
(T) Acrylate and / or formula [2] described below
Compound is included. First , the dental adhesive of the present invention is used.
The novel acrylate compound [1] used will be described.

[0015]

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[1] In the above formula [1], R represents a hydrogen atom or a methyl group. Accordingly, the acrylate compounds provided in the present invention include mesoerythritol monoacrylate and mesoerythritol monomethacrylate.

Such mesoerythritol mono (meth) acrylate can be prepared, for example, as follows. First, mesoerythritol was added to a mixed solution of dimethylformamide and pyridine, and 2,3,5,6-tetramethylhydroquinone and
Add 4-dimethylaminopyridine. While cooling this mixed solution, (meth) acryloyl chloride is gradually added with stirring. The (meth) acryloyl chloride added here is added in an amount of 1 mol or more, preferably 1 to 2 mol per 1 mol of mesoerythritol. After the addition of (meth) acryloyl chloride, the reaction is usually continued for about 5 hours, for example, while gradually returning the temperature of the reaction solution to room temperature. By separating the obtained reaction solution using a separation means such as column chromatography, (meth) acryloyl mesoerythritol [that is, mesoerythritol mono (meth) acrylate] can be obtained. The (meth) acrylate compound thus obtained is mainly composed of 1- O-
(Meth) acryloyl mesoerythritol. Such mesoerythritol mono (meth) acrylate is preferably stored in a small amount of hydroquinone.

[0018] The dental adhesive of the present invention comprises the above-mentioned mesoerythritol mono (meth) acrylate and / or pentaerythritol mono (meth) represented by the following formula [2].
An acrylate and a polymerizable monomer having at least one olefinic double bond copolymerizable with these mono (meth) acrylate compounds.

[0019]

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In the above formula [2], R represents a hydrogen atom or a methyl group. The pentaerythritol mono (meth) acrylate used here can be prepared, for example, by using pentaerythritol instead of mesoerythritol in the method for preparing mesoerythritol mono (meth) acrylate.

In the present invention, when the term “mono (meth) acrylate compound” is used without particular limitation, it is meant to include both compounds represented by the formulas [1] and [2]. .

Since these mono (meth) acrylate compounds each have three hydroxyl groups in the molecule, the use of this compound makes it possible to obtain the adhesive surface (tooth surface) of the adhesive.
This improves the wettability (affinity) of the dental adhesive, and provides a dental adhesive excellent in adhesiveness to the tooth substance and edge sealing property. The present applicant has already proposed a dental adhesive using glyceryl mono (meth) acrylate having two hydroxyl groups in the molecule (Japanese Patent Application Nos. 2-81768 and 2-81769). Book). Comparing the adhesive containing glyceryl mono (meth) acrylate with the adhesive of the present invention containing a mono (meth) acrylate compound, the adhesive of the present invention shows that the adhesive, the affinity for the dentin, and the marginal sealing are obtained. It shows even better values for properties such as properties. When an acrylate compound having four or more hydroxyl groups in the molecule is used, properties such as wettability are improved, but properties such as adhesion water resistance tend to be reduced, When viewed comprehensively as a dental adhesive, the balance between adhesion, affinity and marginal sealing is not good.

Among such mono (meth) acrylate compounds, the mesoerythritol mono (meth) acrylate represented by the formula [1] includes mesoerythritol monoacrylate and mesoerythritol monomethacrylate. The pentaerythritol mono (meth) acrylate represented by 2) includes pentaerythritol monoacrylate and pentaerythritol monomethacrylate. In the dental adhesive of the present invention, these can be used alone or in combination.

The polymerizable monomer used in the present invention includes vinyl esters such as (meth) acrylate, (meth) acrylamide, maleate, fumarate and vinyl acetate, styrene and its derivatives, and , Acrylonitrile and vinyl compounds such as acrolein. Among these, (meth) acrylates are preferred.

Examples of (meth) acrylates preferably used in the present invention include methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, and triethylene glycol di (meth) acrylate. ) Acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GMA), trimethylolethanetri (meth) acrylate, penta Erythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate and N, N-dimethylaminoethyl methacrylate can be mentioned.

In the present invention, as the polymerizable monomer,

[0027]

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At least one kind of polar group represented by the formula:
An acidic polymerizable monomer having at least one olefinic double bond is preferably used. Examples of such acidic polymerizable monomers include the compounds described below.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The dental adhesive of the present invention is, as described above,
The dental adhesive is formed from a (meth) acrylate compound and a polymerizable monomer (preferably an acidic polymerizable monomer) copolymerizable with the (meth) acrylate compound. It can be used in such a mode.

(A) a (meth) acrylate compound,
Used as a mixture with a polymerizable monomer having at least one olefinic double bond copolymerizable with the (meth) acrylate compound (preferably, a part thereof includes the above-mentioned acidic polymerizable monomer). I do. In this case, a third component such as a solvent, a filler, and a polymerization initiator can be added to the mixture as needed.

In the adhesive comprising such a mixture, the (meth) acrylate compound is based on the total weight.
0.01 to 50% by weight (more preferably 0.1 to 30% by weight)
It is preferably contained in an amount of% by weight. The acidic polymerizable monomer is preferably contained in an amount of 0.01 to 50% by weight (more preferably 0.1 to 30% by weight).

The dental adhesive constructed as described above in (a) is a one-part type compared to the dental adhesive constructed as shown in (b) below, and is easy to handle. Yes,
Further, there is no practical problem with regard to storage stability, and it can be used.

The dental adhesive of the present invention, which is used in the form of such a mixture, is used by applying it to teeth, particularly dentin. (B) A composition [A] containing a (meth) acrylate compound and a polymerizable monomer having at least one olefinic double bond copolymerizable with the (meth) acrylate compound (preferably acidic polymerization) And the composition [B] containing the (active monomer) are separately packaged and stored so that both components do not come into contact with each other. That is, the package of the composition [A] and the package of the composition [B] are separately stored, and the composition [A] and the composition [B] are used in a mixed state before use. . Further, the package of the composition [A] and the package of the composition [B]
During storage, the composition [A] and the composition [B] may be stored such that they do not come into contact with each other, and the package may be removed and mixed immediately before use so that both compositions come into contact with each other.

That is, in the former case, the dental adhesive is applied such that the composition [A] is first applied to the tooth material, particularly the dentin (the adhered surface), and then the composition [B] is laminated. Used as In the latter case, the respective packages are removed immediately before use, and the contents are mixed and used.

Composition [A] used in such an embodiment
May contain, in addition to the (meth) acrylate compound, a solvent having a boiling point of 200 ° C. or less at normal pressure, for example, a volatile organic solvent, water, or a mixture thereof. Further, the composition [A] may contain a polymerization initiator, a filler and the like as necessary. In the composition [A],
The (meth) acrylate compound is used in an amount of 0.
It is preferably contained in an amount of 1 to 80% by weight (more preferably 1 to 50% by weight).

The composition [B] usually contains a polymerization initiator in addition to the above polymerizable monomers. Further, the composition [B] may contain a solvent, a filler, and the like, if necessary. The composition [B]
May be of a two-part packaging type as required.

The acidic polymerizable monomer in the composition [B] is 0.01 to 50% by weight (more preferably 0.1 to 50% by weight).
(1 to 30% by weight). In the above embodiment, the usage ratio (weight) of the composition [A] to the composition [B] is set in the range of 1: 100 to 10: 1 (more preferably, 1:10 to 2: 1). preferable.

In the dental adhesive of the present invention, a solvent having a specific temperature or lower can be blended. Examples of such a solvent include water having a boiling point of 100 ° C. at normal temperature and a volatile organic solvent having a boiling point of 200 ° C. or less at normal pressure. Examples of such volatile organic solvents include alcohols such as methanol, ethanol, allyl alcohol, isopropanol and 1-octanol; ketones such as acetone, methyl ethyl ketone and holone; ethyl ether, 1,4-dioxane and diethylene glycol Ethers such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate; and hexane, undecane, toluene, xylene, methylene chloride, 1,2-dichloroethane and 1,1,
2,2-tetrachloroethane and the like can be mentioned. Water or the volatile organic solvent can be used alone, or can be used as a mixture.

The dental adhesive of the present invention may contain a polymerization initiator. Examples of such a polymerization initiator include a benzoyl peroxide-aromatic tertiary amine-based mixture and cumene hydro- Peroxides such as peroxides; tributylborane, aromatic sulfinic acid (or a salt thereof) -aromatic secondary or tertiary amine-acyl peroxide-based mixture, and the like. further,
Examples include α-diketones (eg, camphorquinone, diacetyl, benzyl) -reducing agents (eg, tertiary amines, aldehydes, mercaptans) and photopolymerization initiators such as benzoin methyl ether.

Examples of fillers that can be blended in the dental adhesive of the present invention include inorganic fillers such as glass, quartz, hydroxyapatite, calcium carbonate, barium sulfate, aluminum oxide, titanium oxide and zirconium oxide. Polymer powders such as polymethyl methacrylate powder, polystyrene powder and polyvinyl chloride powder can be mentioned.

The dental adhesive of the present invention can be used in the same manner as a commonly used dental adhesive.
That is, for example, the dental adhesive of the present invention is applied to the surface of the tooth to be bonded, and then a dental restorative material such as a composite resin or metal is arranged on the surface where the dental adhesive is applied, The adhesive is cured to adhere the tooth material to the dental restorative material.

[0060]

According to the present invention, there is provided a novel acrylate compound, mesoerythritol mono (meth) acrylate.

The dental adhesive according to the present invention has excellent adhesiveness to teeth, particularly dentin, and also excellent sealing of the margin between the tooth and the restoration material. Therefore, the dental adhesive of the present invention can be used for various dental applications in which such effects are required, but is particularly suitable for restoration of teeth having erosion, particularly restoration including a cervical region. Used for

Hereinafter, the content of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0063]

Example 1 [Preparation of 1- O -methacryloyl mesoerythritol] Mesoerythritol ( MESO- Erythritol) 1 as a powder
2.211 g (0.100 mol) was added to dimethylformamide (dim.
ehtylformamide (hereinafter "DMF") 60 ml and pyridine (pyridi
ne) was suspended in a mixture with 15 ml (14.73 g, 0.186 mol), and 4-dimethylaminopyridine (dimethylaminopyridine,
(Hereinafter "DMAP") 200 mg and 100 mg of 2,3,5,6-tetramethylhydroquinone (2,3,5,6-tetramethylhydroquinone) are added, and the whole mixture is heated while shaking on a water bath at about 40 ° C. Thereby, a substantially uniform solution can be obtained. When this solution is cooled to 0 to 5 ° C. while stirring in ice water, a small amount of crystals precipitate.

The solution was kept at a temperature of 5 ° C. or lower, and methacryloyl chloride (met) was added to the solution while stirring was continued.
13.1 ml (14.0 g, 0.134 mol) of hacryloyl chloride are added dropwise little by little. When about 3 ml of the reagent is added dropwise, the precipitated crystals are completely dissolved and become a pale yellow uniform liquid. The dropwise addition was completed over 2 hours and 30 minutes, and the slightly yellow transparent reaction solution was gradually returned to room temperature while stirring, and stirring was continued for another 5 hours.

The reaction solution is evaporated on a water bath at 40 ° C. or lower under reduced pressure to give a pale yellow syrupy residue. This is dissolved in 30 ml of a mixed solution of chloroform and ethanol, and purified by column chromatography using 150 g of silica gel.

A mixture of chloroform and ethanol (CHC
l ₃ : EtOH = 95: 5) and collect the effluent which gives a single spot near Rf = 0.3 by thin layer chromatography (developing solvent; CHCl ₃ : EtOH = 95: 5). Removal of the solvent yields about 3.5-5.5 g of a colorless oil.

The infrared absorption spectrum of the obtained reaction product was measured by the KBr tablet method. In addition, 4
Using a 00 megacycle nuclear magnetic resonance spectrometer,
Tetramethylsilane as an internal standard, in dimethylsulfoxide -d ₆ solvent was analyzed by ¹ H-NMR spectrum.

The main peaks of the infrared absorption spectrum and their assignments are as follows. ν KBr (cm ^-1 ): 3400 (-OH), 1707
(Ester, C = O), 1640 (C = O), 1190
The peaks of the (ester, C—O—C) ¹ H-NMR spectrum and their assignments are as follows.

Δ (ppm in DMSO-d₆): 1.88 (3
H, s, = CCH ₃  ), 3.40 (2H, m, -CH
_Two -OH), 3.55 (1H, m, -CH-OH), 3.
61 (1H, m, -CH-OH), 4.04 (1H, d
d, J = 7Hz, 11Hz, COO-CH−), 4.2
4 (1H, dd, J = 3Hz, 11Hz, COO-CH
−), 5.65 (1H, s, = CH), 6.06 (1
H, s, = CH) From the above analysis results, the product is only the hydroxyl group at position 1.
Is esterified 1-O-Methacryloyl mesoerythrit
Is confirmed. This 1-O-Methacryloyl
For mesoerythritol, add a small amount of hydroquinone
Can be stored stably for a long time.

The above reaction is represented by the following formula.

[0071]

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[Test of Adhesion Property] The flat surface of the extracted human dentin treated by polishing the surface with ^# 1000 abrasive paper and then treated with an aqueous solution of EDTA having a concentration of 0.5 mol / liter for 60 seconds, was treated with 1- O -methacryloyl. A composition [A-1] consisting of 35 parts by weight of mesoerythritol and 65 parts by weight of water was applied,
Air blow.

Next, a commercially available dental adhesive (Clearfill New Bond, manufactured by Kuraray Co., Ltd.) containing 10-methacryloyloxydecyldihydrodiene phosphate was applied to the coated surface, followed by air blowing. Commercially available composite resin clearfill FII (Kuraray Co., Ltd.)
Made) and cured.

The ten samples prepared as described above were immersed in water at 37 ° C. for 24 hours, and then the tensile adhesive strength was measured. The results are shown in Table 1.

The enamel on the adjacent surface of 10 extracted molars was removed, and dentin flattened with ^# 1000 abrasive paper was added with a diameter of 3 mm.
A 1.5 mm deep cylindrical cavity was formed. Next, the inside of the cavity was treated with an aqueous solution of EDTA having a concentration of 0.5 mol / liter for 60 seconds, washed and dried, and then the composition [A-1] was applied to the entire cavity and air blown. After applying Clearfill New Bond and air blowing, Clearfill FII
Were filled into the cavities and allowed to cure.

Immediately immersed in water at room temperature and allowed to stand for 10 minutes, the filling portion was mirror-polished to expose the cavity, and the gap between the cavity and the interface between the filling material and the optical microscope (NIKON, OPTIPHOTO, × 400).
Observed using.

For eight of the ten samples, no gap was observed over the entire periphery of the fossa, indicating a good bonding state. The width of the shrinkage gap for all samples is 0-0.06
μm, and the average value was 0.01 ± 0.01 μm.

[0078]

Example 2 Example 1 was repeated except that composition [A-2] consisting of 40 parts by weight of 1- O -methacryloyl mesoerythritol and 60 parts by weight of water was used instead of composition [A-1]. Similarly, the adhesive strength and the width of the shrinkage gap were measured.

The results are shown in Table 1. In addition, for all of the ten samples, no gap was observed over the entire periphery of the fossa margin, indicating a good bonding state.

[0080]

Example 3 [Preparation of 1- O -methacryloyl pentaerythritol] pentaerythritol 1 as a powder
3.615 g (0.100 mol) was added to 60 ml of DMF and pyridine (p
yridine) was suspended in a mixture of 15 ml (14.73 g, 0.186 mol), and 200 mg of DMAP was added to 100 ml of 2,3,5,6-tetramethylhydroquinone (2,3,5,6-tetramethylhydroquinone).
g and warm the whole mixture with shaking on a water bath at about 40 ° C. A nearly homogeneous solution is obtained. When this solution is cooled to 0 to 5 ° C. while stirring in ice water, a small amount of crystals precipitate.

The solution was kept at a temperature of 5 ° C. or lower, and methacryloyl chloride (met) was added to the solution while stirring was continued.
13.1 ml (14.0 g, 0.134 mol) of hacryloyl chloride are added dropwise little by little. When about 3 ml of the reagent is added dropwise, the precipitated crystals are completely dissolved and become a pale yellow uniform liquid. The dropwise addition was completed over 2 hours and 30 minutes, and the slightly yellow transparent reaction solution was gradually returned to room temperature while stirring, and stirring was continued for another 5 hours.

The reaction solution is evaporated on a water bath at 40 ° C. or lower under reduced pressure to give a pale yellow syrupy residue. This is dissolved in 30 ml of a mixed solution of chloroform and ethanol, and purified by column chromatography using 150 g of silica gel.

A mixture of chloroform and ethanol (CHC
l ₃ : EtOH = 95: 5) and collect the effluent which gives a single spot near Rf = 0.3 by thin layer chromatography (developing solvent; CHCl ₃ : EtOH = 90: 10). Removal of the solvent yields about 3.6-5.2 g of a colorless oil.

The infrared absorption spectrum of the obtained reaction product was measured by the KBr tablet method. In addition, 4
Using a 00 megacycle nuclear magnetic resonance spectrometer,
Tetramethylsilane as an internal standard, in dimethylsulfoxide -d ₆ solvent was analyzed by ¹ H-NMR spectrum.

The main peaks of the infrared absorption spectrum and their assignments are as follows. ν KBr (cm ^-1 ): 3400 (-OH), 1710
(Ester, C = O), 1635 (C = O), 1200
The peaks of the (ester, C—O—C) ¹ H-NMR spectrum and their assignments are as follows.

Δ (ppm in DMSO-d ₆ ): 1.89 (3
H, s, = C-C H 3), 3.39 (6H, d, -C H
₂ -OH × 3, D ₂ O → s), 3.98 (2H, s, -C
_{OO-C H 2 -),} 5.63 (1H, s, = C- H),
6.2 (1H, s, = C- H ) From the above analysis results, it was confirmed that the product was 1- O -methacryloylpentaerythritol in which only one hydroxyl group at the 1-position was esterified. . This 1- O -methacryloylpentaerythritol can be stably stored for a long period of time by adding a small amount of hydroquinone.

The above reaction is represented by the following formula.

[0088]

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[Adhesion Test] The surface was polished with a ^# 1000 abrasive paper, and then the ED having a concentration of 0.5 mol / liter was used.
A composition [A-3] consisting of 20 parts by weight of 1- O -methacryloylpentaerythritol and 80 parts by weight of water was applied to a flat surface of the extracted human dentin treated with a TA aqueous solution for 60 seconds, and air blown.

Next, a commercially available dental adhesive (Clearfill New Bond, manufactured by Kuraray Co., Ltd.) containing 10-methacryloyloxydecyldihydrodiene phosphate was applied to the coated surface, followed by air blowing. Commercially available composite resin clearfill FII (Kuraray Co., Ltd.)
Made) and cured.

The ten samples prepared as described above were immersed in water at 37 ° C. for 24 hours, and the tensile adhesive strength was measured. The results are shown in Table 1.

The enamel on the adjacent surface of 10 extracted molars was removed, and a cylindrical cavity having a diameter of 3 mm and a depth of 1.5 mm was formed in dentin flattened with ^# 1000 abrasive paper. Then
The cavity was treated with an aqueous solution of EDTA having a concentration of 0.5 mol / liter for 60 seconds, washed with water and dried, and then the composition [A-3] was applied to the entire cavity and air blown. Further, a clearfill new bond was applied, and after air blowing, the cavity was filled with clearfill FII and cured.

Immediately immersed in water at room temperature and left for 10 minutes, the filling portion was mirror-polished to expose the cavity, and the gap between the cavity and the filler interface was observed using an optical microscope (NIKON, OPTIPHOTO × 400). .

Although a gap was observed around the entire periphery of the fossa of the ten samples, a good bonding condition was exhibited. The width of the shrinkage gap for all samples was 0.03-0.17 μm, and the average was 0.08 ± 0.05 μm.

[0095]

Example 4 In Example 3, a composition [A-4] consisting of 35 parts by weight of 1- O -methacryloylpentaerythritol and 65 parts by weight of water was used in place of the composition [A-3]. Similarly, the adhesive strength and the width of the shrinkage gap were measured.

The results are shown in Table 1. 5 out of 10 samples
Regarding the individual, no gap was observed over the entire periphery of the fossa, showing a good bonding state. The width of the shrinkage gap for all samples is 0-0.04 μm, and the average value is 0.01
± 0.01 μm.

[0097]

Example 5 In Example 3, except that the composition [A-5] consisting of 40 parts by weight of 1- O -methacryloylpentaerythritol and 60 parts by weight of water was used instead of the composition [A-3]. Similarly, the adhesive strength and the width of the shrinkage gap were measured.

The results are shown in Table 1. 5 out of 10 samples
Regarding the individual, no gap was observed over the entire periphery of the fossa, showing a good bonding state. The width of the shrinkage gap for all samples was 0-0.08 μm, and the average was 0.02 μm.
± 0.03 μm.

[0099]

Example 6 Example 3 was repeated except that composition [A-6] consisting of 45 parts by weight of 1- O -methacryloylpentaerythritol and 55 parts by weight of water was used instead of composition [A-3]. Similarly, the adhesive strength and the width of the shrinkage gap were measured.

The results are shown in Table 1. 5 out of 10 samples
Regarding the individual, no gap was observed over the entire periphery of the fossa, showing a good bonding state. The width of the shrinkage gap for all samples is 0-0.06 μm, and the average value is 0.02 μm.
± 0.02 μm.

[0101]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Miyasaka Sada 1-27-11 Aobadai, Midori-ku, Yokohama-shi, Kanagawa Prefecture (56) References JP-A-3-21603 (JP, A) JP-A-3-239263 ( JP, A) Hiromasa Kato et al., Journal of Showa Dental Society, 1984, p. 172-184 (58) Fields investigated (Int. Cl. ⁶ , DB name) A61K 6/00 A61K 6/083 500 C07C 69/54 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A mesoerythritol mono (meth) acrylate represented by the following formula [1] and / or the following formula [2]:
A pentaerythritol mono (meth) acrylate represented by the formula: and a polymerizable monomer having at least one olefinic double bond copolymerizable with the (meth) acrylate compound. Adhesive; Embedded image (However, in the formulas [1] and [2], R represents a hydrogen atom or a methyl group). 2. The dental adhesive according to claim 1, wherein the adhesive comprises mesoerythritol mono (meth) acrylate and / or pentaerythritol mono (meth) acrylate and at least one olefinic copolymer copolymerizable with the mono (meth) acrylate compound. The dental adhesive according to claim 1, wherein the adhesive is a one-package mixture with a polymerizable monomer having a heavy bond. 3. The dental adhesive according to claim 1 , wherein the adhesive component contains mesoerythritol mono (meth) acrylate and / or pentaerythritol mono (meth) acrylate, and at least one copolymerizable with the mono (meth) acrylate compound. 2. An adhesive component containing a polymerizable monomer having two olefinic double bonds is separately packaged, and both components are held in a non-contact state. Dental adhesive. 4. The method according to claim 1, wherein the mesoerythritol mono (meth) acrylate and / or pentaerythritol mono (meth) acrylate are dissolved in a solvent having a boiling point of 200 ° C. or less at normal pressure.
Item 4. The dental adhesive according to any one of Items 3 to 3. 5. The polymerizable monomer according to claim 1, wherein said polymerizable monomer has at least one olefinic double bond and at least one kind of acidic group selected from the following groups. Dental adhesive as described; (However, in the above formula, Z represents a halogen atom,
The bond may be a hydroxyl group, a halogen atom or -PO (O
H) The group represented by -O- is not bonded).