JPH10306058A - New acrylate compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new (meth)acrylate compound excellent in adhesivity, additionally excellent in balance among an edge blocking property, which can suppress the formation of a gap at an edge between a dentine and a repairing material, hydrophilicity of an adhesive, etc., and applicable as a dental adhesive. SOLUTION: A mesoerythritol mono(meth)acrylate of the formula (R is H or methyl), e.g. 1-o-methacryloylmesoerythritol. A compound of the formula is obtained e.g. by adding, to a mixed solution of dimethylformamide and pyridine, mesoerythritol, further 2,3,5,6-tetramethylhydroquinone and 4- dimethylaminopyridine, and subsequently (meth)acryloyl chloride, and making them to react with each other.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acrylate compound having excellent adhesion between dental materials 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.
58-21607), a polymerizable group having a carboxyl group, an acid anhydride group (see JP-A-54-11149) and an acid halide group (see JP-A-57-151607). It is a 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 inventor of the present invention has found that in such a dental adhesive, the number of hydroxyl groups contained in the (meth) acrylate-based polymerizable monomer depends on the performance such as adhesiveness, marginal sealing and hydrophilicity. The present invention has been found to have a great effect on the balance of the present invention.

[0006]

The object of the present invention is to provide not only an excellent adhesive property but also an excellent balance between the marginal sealing property of suppressing the formation of a gap between the tooth material and the restoration material and the hydrophilicity of the adhesive. It is an object of the present invention to provide a novel (meth) acrylate compound that can be used for a dental adhesive.

[0007]

SUMMARY OF THE INVENTION The mesoerythritol mono (meth) acrylate of the present invention is represented by the following formula [1].

[0008]

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However, in the formula [1], R represents a hydrogen atom or a methyl group. The present invention provides a novel mono (meth) acrylate-based compound. This equation [1]
The mono (meth) acrylate compound represented by has both three hydroxyl groups in the molecule. As described above, the dental adhesive containing the mono (meth) acrylate compound having three hydroxyl groups has a very good balance of properties such as adhesiveness, marginal sealing property and hydrophilicity.

[0010]

DETAILED DESCRIPTION OF THE INVENTION First, the novel acrylate compound of the present invention will be described. The acrylate compound provided by the present invention is mesoerythritol mono (meth) acrylate represented by the following formula [1].

[0011]

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However, 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 a 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.

[0014] 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.

[0015]

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In the 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 a molecule (Japanese Patent Application Nos. 2-81768 and 2-81769). Book).

When 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
It shows even better values for properties such as adhesion, affinity for tooth material and marginal sealing. 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; , 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,

[0024]

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At least one 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.

[0026]

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[0027]

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[0028]

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[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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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 shown in (a) above is a one-part type compared to the dental adhesive constructed as shown in (b) below, so that it 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, especially 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 mixed in advance on the adhesive surface before use. To use. Further, the package of the composition [A] and the package of the composition [B] are stored such that the composition [A] and the composition [B] do not come in contact with each other during storage, and the package is immediately stored before use. The package can be removed and mixed so that the composition is in contact.

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 hydrodiamine. Peroxides such as peroxides; and mixtures of tributylborane, aromatic sulfinic acid (or a salt thereof), aromatic secondary or tertiary amine-acyl peroxide, 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 incorporated 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.

[0057]

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 teeth 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 restoring teeth having caries, particularly for restoration including the cervical region. Used.

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

[0060]

Example 1 [Production of 1-O-methacryloyl mesoerythritol] MESO-Erythritol as powder 12.2
11 g (0.100 mol) of dimethylformamide (dimethylf
ormamide, hereafter "DMF") 60ml and pyridine
Suspended in a mixture with 15 ml (14.73 g, 0.186 mol)
200 mg of 4-dimethylaminopyridine (DMAP) and 100 mg of 2,3,5,6-tetramethylhydroquinone (2,3,5,6-tetramethylhydroquinone) are added, and the whole mixture is subjected to a water bath at about 40 ° C. By heating while shaking above, a substantially uniform 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 in small portions. When about 3 ml of the reagent is added dropwise, the precipitated crystals are completely dissolved and become a pale yellow uniform liquid. The dropping 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 giving 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
_2- OH), 3.55 (1H, m, -CH-OH), 3.
61 (1H, m, -CH-OH), 4.04 (1H, dd
 , 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.
1-O-methacryloyl mesoerythritol esterified with
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.

[0068]

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[0069]

[Reference Example 1] [Adhesion test] The surface was polished with # 1000 abrasive paper, and then treated with an EDTA aqueous solution having a concentration of 0.5 mol / L for 60 seconds. -O-methacryloyl mesoerythritol 35 parts by weight and water 65
The composition [A-1] consisting of parts by weight was applied 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, and after air blowing, a commercially available composite was used. Resin Clearfill FII (manufactured by Kuraray Co., Ltd.) was built up 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 the ten 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 and dried, and then the composition [A-1] 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 allowed to stand for 10 minutes, the filled portion was mirror-polished to expose the cavity, and the gap between the cavity and the interface between the cavity and the filler was examined with an optical microscope (NIKON, OPTIPHOTO, × 400).
Observed using.

For eight of the ten samples, 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 was 0.01 ± 0.01 μm.

[0074]

REFERENCE EXAMPLE 2 Except for using the composition [A-2] consisting of 40 parts by weight of 1-O-methacryloyl mesoerythritol and 60 parts by weight of water instead of the composition [A-1] in Reference Example 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.

[0076]

[Example 2] [Production of 1-O-methacryloyl pentaerythritol] pentaerythritol 1 as 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 DMAP 200 mg and 2,3,5,6-tetramethylhydroquinone (2,3,5,6-tetramethylhydroquinone) 100
mg 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 in small portions. When about 3 ml of the reagent is added dropwise, the precipitated crystals are completely dissolved and become a pale yellow uniform liquid. The dropping 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.

[0084]

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[0085]

[Reference Example 3] [Adhesion test] The surface was polished with # 1000 abrasive paper.
Then, a composition consisting of 20 parts by weight of 1-O-methacryloylpentaerythritol and 80 parts by weight of water [A-] was placed on the flat surface of the extracted human dentin treated with an aqueous solution of EDTA at a concentration of 0.5 mol / liter for 60 seconds. 3] was applied 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.) 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 of the adjacent surface of the ten 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, allowed to stand for 10 minutes, and then mirror-polished the filling portion to expose the cavity, and defined the gap between the cavity and the filler interface with an optical microscope (NIKON, OPTIPHOTO × 400).
Observed using.

Although a gap was observed over 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.

[0091]

REFERENCE EXAMPLE 4 A composition was prepared in the same manner as in Reference Example 3, except that the composition [A-4] 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.

[0093]

Reference Example 5 The procedure of Reference Example 3 was repeated, 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.

[0095]

REFERENCE EXAMPLE 6 Except for using the composition [A-6] consisting of 45 parts by weight of 1-O-methacryloylpentaerythritol and 55 parts by weight of water instead of the composition [A-3] in Reference Example 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 0-0.06 μm and the average was 0.02 μm.
± 0.02 μm.

[0097]

[Table 1]

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[Procedure amendment]

[Submission date] June 3, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Detailed description of the invention

[Correction method] Change

[Correction contents]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel acrylate compound having excellent adhesion between dental materials 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.
58-21607), a polymerizable group having a carboxyl group, an acid anhydride group (see JP-A-54-11149) and an acid halide group (see JP-A-57-151607). It is a 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]

The object of the present invention is to provide not only an excellent adhesive property but also an excellent balance between the marginal sealing property of suppressing the formation of a gap between the tooth material and the restoration material and the hydrophilicity of the adhesive. It is an object of the present invention to provide a novel (meth) acrylate compound that can be used for a dental adhesive.

[0007]

SUMMARY OF THE INVENTION The mesoerythritol mono (meth) acrylate of the present invention is represented by the following formula [1].

[0008]

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However, in the formula [1], R represents a hydrogen atom or a methyl group. The present invention provides a novel mono (meth) acrylate-based compound. This equation [1]
The mono (meth) acrylate compound represented by has both three hydroxyl groups in the molecule. As described above, the dental adhesive containing the mono (meth) acrylate compound having three hydroxyl groups has a very good balance of properties such as adhesiveness, marginal sealing property and hydrophilicity.

[0010]

DETAILED DESCRIPTION OF THE INVENTION First, the novel acrylate compound of the present invention will be described. The acrylate compound provided by the present invention is mesoerythritol mono (meth) acrylate represented by the following formula [1].

[0011]

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However, 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 a 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 [namely, 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.

The dental adhesive using the above acrylate compound of the present invention is the above-mentioned mesoerythritol mono (meth) acrylate or pentaerythritol mono (meth) acrylate represented by the following formula [2]: and mixtures <br/> of, are generally prepared from these mono (meth) acrylate compound copolymerizable with at least one olefinic double bond with a polymerizable monomer.

[0015]

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In the 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.

Since these mono (meth) acrylate compounds each have three hydroxyl groups in the molecule, the use of this compound makes it possible to bond the adhesive to the surface to be bonded (tooth surface).
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 a molecule (Japanese Patent Application Nos. 2-81768 and 2-81769). Book).

[0018] and adhesives containing the glyceryl mono (meth) acrylate, is compared with the adhesive of the present invention comprising a mono (meth) acrylate compounds, the present invention described above acrylate
Adhesives using rate compounds show even better values for properties such as adhesion, affinity for tooth material and marginal sealing. 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 dental adhesives, these can be used alone or in combination.

Examples of the polymerizable monomer used for the dental adhesive include (meth) acrylic acid ester, (meth) acrylamide, maleic acid ester, vinyl ester such as fumaric acid ester and vinyl acetate, styrene and its derivatives. And vinyl compounds such as acrylonitrile and acrolein. Among these, (meth) acrylates are preferred.

Examples of (meth) acrylic acid esters preferably used include methyl (meth) acrylate, 2- (meth) acrylate,
Hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis [4- (3-methacryloyloxy-2-hydroxy) Propoxy) phenyl] propane (Bis-GMA), trimethylolethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate and N, N-dimethylaminoethyl methacrylate.

In the dental adhesive , as a polymerizable monomer,

[0023]

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At least one 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.

[0025]

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[0026]

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[0027]

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[0028]

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[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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The dental adhesive is, as described above, a (meth)
The dental adhesive is formed from an acrylate compound and a polymerizable monomer (preferably an acidic polymerizable monomer) copolymerizable with the (meth) acrylate compound.
For example, it can be used in the following modes.

(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 used in the form of such a mixture is used by applying it to teeth, especially 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 mixed in advance on the adhesive surface before use. To use. Further, the package of the composition [A] and the package of the composition [B] are stored such that the composition [A] and the composition [B] do not come in contact with each other during storage, and the package is immediately stored before use. The package can be removed and mixed so that the composition is in contact.

That is, in the former case, the dental adhesive is applied so 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, a solvent at 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; esters such as ethyl acetate, butyl acetate and 2-ethylhexyl acetate;
And hexane, undecane, toluene, xylene,
Methylene chloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane and the like can be mentioned. Water or the volatile organic solvent can be used alone,
They can also be used as a mixture.

The dental adhesive may contain a polymerization initiator. Examples of such a polymerization initiator include a benzoyl peroxide-aromatic tertiary amine-based mixture and cumene hydroperoxide. Peroxide of
Tributylborane, aromatic sulfinic acid (or a salt thereof) -aromatic secondary or tertiary amine-acyl peroxide-based mixture, and the like. Additionally, α-diketones (eg, camphorquinone, diacetyl, benzyl) -reducing agents (eg, tertiary amines, aldehydes,
Mercaptans) and benzoin methyl ether.

Examples of fillers that can be incorporated into the dental adhesive include inorganic fillers such as glass, quartz, hydroxyapatite, calcium carbonate, barium sulfate, aluminum oxide, titanium oxide and zirconium oxide, and polymethyl methacrylate. Powders, polymer powders such as polystyrene powder and polyvinyl chloride powder can be mentioned.

The dental adhesive using the acrylate compound of the present invention can be used in the same manner as a commonly used dental adhesive. That is, for example, apply the dental adhesive of the present invention to the surface of the tooth to be bonded,
A dental restorative material such as a composite resin or a metal is placed on the surface on which the dental adhesive is applied, and the adhesive is cured to bond the tooth material and the dental restorative material.

[0056]

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

The acrylate compound according to the present invention
Dental adhesives with is excellent in sealing ability of the margins of the tooth and the restorative material has excellent adhesion to tooth structure particularly dentin. Therefore, the dental adhesive can be used for various dental applications where such effects are required, and is particularly preferably used for restoring teeth having erosion, particularly for restoration including the cervical region.

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

[0059]

[Example 1] [Production of 1- O -methacryloyl mesoerythritol] MESO-Erythritol as powder 12.2
11 g (0.100 mol) of dimethylformamide (dimethylf
ormamide, hereafter "DMF") 60ml and pyridine
Suspended in a mixture with 15 ml (14.73 g, 0.186 mol)
200 mg of 4-dimethylaminopyridine (DMAP) and 100 mg of 2,3,5,6-tetramethylhydroquinone (2,3,5,6-tetramethylhydroquinone) are added, and the whole mixture is subjected to a water bath at about 40 ° C. By heating while shaking above, a substantially uniform 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 in small portions. When about 3 ml of the reagent is added dropwise, the precipitated crystals are completely dissolved and become a pale yellow uniform liquid. The dropping 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 giving 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.

An infrared absorption spectrum of the obtained reaction product was measured by a 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
_2- OH), 3.55 (1H, m, -CH-OH), 3.
61 (1H, m, -CH-OH), 4.04 (1H, dd
 , 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.

[0067]

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[0068]

[Reference Example 1] [Adhesion test] The surface was polished with # 1000 abrasive paper, and then treated with an EDTA aqueous solution having a concentration of 0.5 mol / L for 60 seconds. - O - methacryloyl mesoerythritol 35 parts by weight of water 65
The composition [A-1] consisting of parts by weight was applied 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, and after air blowing, a commercially available composite was used. Resin Clearfill FII (manufactured by Kuraray Co., Ltd.) was built up 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 of the adjacent surface of the ten 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 and dried, and then the composition [A-1] 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 allowed to stand for 10 minutes, after which the filling portion was mirror-polished to expose the cavity, and the gap between the cavity and the interface between the cavity and the filler was examined with an 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.

[0073]

REFERENCE EXAMPLE 2 Except that the composition [A-1] was replaced by the composition [A-2] consisting of 40 parts by weight of 1- O -methacryloyl mesoerythritol and 60 parts by weight of water in place of the 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.

[0075]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Sadao Wakumoto 3-43-14-702 Hongo, Bunkyo-ku, Tokyo (72) Inventor Satoshi Miyasaka 1-27-11 Aobadai, Midori-ku, Yokohama-shi, Kanagawa

Claims (1)

[Claims] 1. A mesoerythritol mono (meth) acrylate represented by the following formula [1]: (However, in the formula [1], R represents a hydrogen atom or a methyl group).