JPH0764699B2 - Dental adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in low-temperature curability near room temperature and water-resistant adhesion, and has excellent adhesion of enamel to teeth such as dentin and dental alloys. The present invention relates to a dental adhesive composition having performance and having no adverse effects such as irritation to dental pulp.

[Conventional technology]

Many adhesives for orthodontics or restoration of teeth, which are composed of radically polymerizable monomers such as (meth) acrylate vinyl monomers and catalysts, have been proposed.
A curable composition (Japanese Patent Application Laid-Open No. 60-44508) comprising a (meth) acrylic acid ester vinyl monomer, a (meth) acryloyloxyl group-containing aromatic carboxylic acid (anhydride), an amine and a sulfinic acid (salt), and room temperature And an adhesive composed of a liquid (meth) acrylic acid ester, an amine, a sulfinic acid (salt), and a peroxide (JP-A-53-39331).
No.), MMA, 4-META, and tributylborane (TBB)
Consisting of adhesive (day tooth coercive Journal, 28, 452-478 (1985)), and the like have been reported. However, it has been difficult for conventional adhesives and curable compositions to obtain sufficient adhesion to dentine, particularly to dentin treated with a mild etching agent such as EDTA.

[Problems to be solved by the invention]

The present inventors have excellent low-temperature curability near room temperature and excellent water-resistant adhesiveness, and have excellent adhesion performance to teeth such as enamel, dentin and dental alloys, especially dentin treated with a mild etching agent. As a result of diligent examination of a dental adhesive composition which has an adverse effect such as irritation on dental pulp and is excellent as a dental adhesive in the restoration of teeth, [A] a monofunctional (meth) acrylate-based monomer, [B] Specific polyfunctional (meth) acrylate-based monomer,
The present inventors have found that a dental adhesive composition comprising [C] a specific acidic group-containing (meth) acrylate-based monomer and [D] trialkylboron or an oxide thereof can achieve the above objects, and have reached the present invention.

[Means for Solving Problems] and [Function] According to the present invention, [A] a monofunctional (meth) acrylate-based monomer, [B] a general formula [I] [In the formula, R ¹ represents a divalent aromatic residue having at least one aromatic ring and optionally having an oxygen atom or a sulfur atom in the molecule, and R ² and R ³ are respectively A hydrogen atom or a methyl group, and n and m are positive integers], [C] at least one (meth) acryloyloxyl group in one molecule. Provided is a dental adhesive composition containing an acidic group-containing (meth) acrylate-based monomer and [D] trialkylboron or an oxide thereof.

The monofunctional (meth) acrylate-based monomer [A] used in the dental adhesive composition of the present invention may contain a functional group other than an acidic group in its molecule. (Meth) acrylate, ethyl (meth) acrylate,
Butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl-hexyl (meth) acrylate,
A hydrocarbon group-containing (meth) acrylate such as dodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate,
Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monododecyl ether Ethylene glycol unit-containing (meth) acrylates such as (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, trifluoroethyl (meth) acrylate, Fluorine substituent-containing (meth) acrylates such as perfluorooctyl (meth) acrylate, γ- (meth Examples thereof include silane-based (meth) acrylates such as acryloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropyltri (trimethylsiloxy) silane, and tetrahydrofurfuryl (meth) acrylate, which may be used alone or in combination of two or more. Can be mixed and used. Among these, methyl (meth) acrylate and ethyl (meth)
Alkyl (meth) acrylates such as acrylate, hexyl (meth) acrylate and dodecyl (meth) acrylate or hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable, and particularly Methyl methacrylate, n-hexyl methacrylate,
It is preferable to use 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate alone or a mixture thereof.

The polyfunctional (meth) acrylate monomer [B] used in the dental adhesive composition of the present invention has the general formula [I]. [In the formula, R ¹ represents a divalent aromatic residue having at least one aromatic ring and optionally having an oxygen atom or a sulfur atom in the molecule, and R ² and R ³ are respectively A hydrogen atom or a methyl group, and n and m are positive integers].
In the general formula [I] representing the polyfunctional (meth) acrylate-based monomer [B], specifically as the divalent aromatic residue, Etc. can be illustrated. Of these, Specifically as the polyfunctional (meth) acrylate-based monomer, Can be illustrated, in particular Is preferred. A mixture of two or more of these polyfunctional methacrylates can also be used.

As the acidic group-containing (meth) acrylate-based monomer [C] containing at least one (meth) acryloyloxyl group in one molecule used in the dental adhesive composition of the present invention, Aromatic polycarboxylic acid containing at least one (meth) acryloyloxyl group or its acid anhydride (C ₁ ) or phosphoric acid or sulfone containing at least one (meth) acryloyloxyl group in one molecule Partial ester of acid (monoester of phosphoric acid,
And diesters or mixtures thereof, sulfonic acid monoesters) and the like (C ₂ ). More specifically, the aromatic polycarboxylic acid (C ₁ ) containing at least one (meth) acryloyloxyl group in one molecule, more specifically, has at least two hydroxyl groups in one molecule and has an oxygen atom. At least one hydroxyl group in the alkane polyol which may be contained forms an ester of (meth) acrylic acid, and at least one hydroxyl group has one carboxyl group and at least three carboxyl groups. Examples thereof include (meth) acryloyloxyl group-containing aromatic polycarboxylic acid having a structure in which an ester is formed with the carboxyl group or its anhydride. Among the aromatic polycarboxylic acids having at least 3 carboxyl groups, an aromatic compound in which at least 2 carboxyl groups among at least 3 or more carboxyl groups are bonded to adjacent carbon atoms on the aromatic nucleus. It is preferable to be a polycarboxylic acid, specifically, hemimellitic acid, trimellitic acid, prenitic acid,
Examples thereof include melophanic acid and pyromellitic acid.

Examples of the (meth) acryloyloxyl group-containing aromatic polycarboxylic acid or acid anhydride thereof include 4- (meth) acryloyloxymethoxycarbonylphthalic acid or acid anhydride thereof, 4- (meth) acryloyloxyethoxycarbonylphthalic acid or Its acid anhydride, 4- (meth) acryloyloxybutoxycarbonylphthalic acid or its acid anhydride, 4- [2-hydroxy-3- (meth) acryloyloxypropoxycarbonyl] phthalic acid or its acid anhydride, 2,3-bis (3,4-dicarboxybenzoyloxy)
Propyl (meth) acrylate or its acid anhydride 2-
Examples thereof include (3,4-dicarboxybenzoyloxy) 1,3-dimethacryloyloxypropane and acid anhydrides thereof.

Also, as a partial ester of phosphoric acid or sulfonic acid containing at least one (meth) acryloyloxyl group in one molecule (monoester of phosphoric acid, diester or mixture thereof, monoester of sulfonic acid) (C ₂ ). Specifically, 2- (meth) acryloyloxyethylphenyl acid phosphate, bis [2- (meth) acryloyloxyethyl] acid phosphate, bis [3-
(Meth) acryloxypropyl] acid phosphate,
2- (meth) acryloyloxyethylphenylphosphonate, And the like.

Among these acidic group-containing (meth) acrylate-based monomers [C] containing at least one (meth) acryloyloxyl group in one molecule, at least one (meth) acryloyloxyl in one molecule An aromatic polycarboxylic acid containing a group or an acid anhydride thereof (C ₁ ) is preferable, and among these, 4- (meth) acryloyloxyethoxycarbonylphthalic acid or an acid anhydride thereof is preferable, and 4-methacryloyloxy is particularly preferable. Adhesion to teeth using ethoxycarbonylphthalic anhydride
It is preferable because water resistance and durability are improved.

Specific examples of the trialkylboron or its oxide [D] used in the dental adhesive composition of the present invention include triethylboron, tripropylboron, triisopropylboron, tri-n-butylboron and tri-n. It is possible to use amylboron, triisoamylboron, tri-sec-amylboron or a trialkylboron oxide in which a part thereof is oxidized. Among these, Tri-n
Preference is given to using butylboron or its partial oxides.

The monofunctional (meth) acrylate monomer [A] and the polyfunctional (meth) compounded in the dental adhesive composition of the present invention
The mixing ratio of the acrylate-based monomer [B] is not particularly limited, but is usually 5 to 95% by weight of the monofunctional (meth) acrylate-based monomer [A] and the polyfunctional (meth) acrylate-based monomer [B] 95. To 5% by weight, preferably 10 to 95% by weight of monofunctional (meth) acrylate-based monomer [A], 90 to 5% by weight of polyfunctional (meth) acrylate-based monomer [B], particularly preferably monofunctional When the (meth) acrylate-based monomer [A] is in the range of 25 to 90% by weight and the polyfunctional (meth) acrylate-based monomer [B] is in the range of 75 to 10% by weight, the adhesive force to teeth and water resistance, especially Etching treatment on dentin is preferable because it shows high adhesive strength and water resistance even when a mild acid such as ETDA is used.

The amount of the acidic group-containing (meth) acrylate-based monomer [C] blended in the dental adhesive composition of the present invention is the same as that of the monofunctional (meth) acrylate-based monomer [A] and The amount is usually 1 to 50 parts by weight, preferably 3 to 30 parts by weight, and particularly preferably 5 to 15 parts by weight, based on 100 parts by weight of the polyfunctional (meth) acrylate-based monomer [B].

Furthermore, the compounding amount of the trialkylboron or its oxide [D] compounded in the dental adhesive composition of the present invention is such that the monofunctional (meth) acrylate monomer [A] and the polyfunctional (meth) ) Generally 2 to 100 parts by weight, preferably 5 to 70 parts by weight, particularly preferably 100 parts by weight of the acrylate-based monomer [B] and the acidic group-containing (meth) acrylate-based monomer [C]. It is in the range of 5 to 50 parts by weight. The trialkylboron or its oxide [D]
Is usually the (meth) acrylate-based monomer [A],
When mixed with [B] and [C], the polymerization reaction starts within a few seconds to several tens of minutes. Therefore, it should be stored separately from [A], [B] and [C] just before use. Mixed in.

In addition to the above-mentioned essential components, the dental adhesive composition of the present invention may optionally contain other components, such as other polymerizable monomers such as polyfunctional (meta-functional) compounds having at least one urethane bond in one molecule. ) Acrylate-based monomer, powdered inorganic filler,
An organic polymer, a polymerization inhibitor, etc. can be blended. Specific examples of the powdery inorganic filler include kaolin, talc, clay, calcium carbonate, silica, silica-alumina, alumina, titanium oxide, calcium phosphate, glass powder and quartz powder. Examples of the organic polymer include wax, ethylene / vinyl acetate copolymer, polymethyl acrylate, polymethyl methacrylate and copolymers thereof. The mixing ratio of these components is appropriate.

〔The invention's effect〕

The dental adhesive composition of the present invention is excellent in low-temperature curability near room temperature and water-resistant adhesiveness, and is a tooth substance such as enamel or dentin or a dental alloy, particularly dentin treated with a mild etching agent. Since it has excellent adhesive properties to teeth and has no irritation to pulp, it is used as a bonding agent for dental composites resin, hard resin and other dental adhesive compositions. Can be used. Among these, it is most preferable to use it as a bonding agent for dental composite resin.

〔Example〕

 Next, the present invention will be specifically described with reference to examples.

The method for evaluating the dental adhesive composition of the present invention and the production examples of the photocurable composites resin used in Examples and Comparative Examples are shown below. The following abbreviations used in the following Examples and Comparative Examples respectively represent the following compounds.

MMA ・ ・ ・ Methyl Methacrylate HMA ・ ・ ・ n-Hexyl Methacrylate HEMA ・ ・ 2-Hydroxyethyl Methacrylate HPMA ・ ・ 2-Hydroxypropyl Methacrylate TBB ・ O ・ ・ ・ Partial oxide of tri-n-butylboron BPO ・ ・ ・ Benzoyl peroxide DEPT ・ ・ ・ ・ Diethanol paratoluidine PTSNa ・ ・ ・ Sodium paratoluene sulfinate PMMA ・ ・ ・ ・ Polymethyl Methacrylate HQME ・ ・ ・ ・ Hydroquinone monomethyl ether (I) Evaluation method of adhesive strength # 600 d
Polish it well with merry paper, smooth the surface, and then
Melt is 65% phosphoric acid aqueous solution for 30 seconds, dentin is 0.3M EDTA
・ Etching treatment with 2Na-0.2M EDTA ・ Fe ・ Na aqueous solution for 60 seconds
Made sense. After sufficiently washing with water, air the etching surface.
Blow and dry, and then the cell with a hole with a diameter of 5 mm.
I put on Rohan tape (about 13mm x 13mm). Example or
Apply the bonding agent described in Comparative Example to the circular hole to
Teflon mold matched with the circular hole by air blowing
(Cylinder with a diameter of 5 mm and a depth of 2 mm)
Filled with gitutrezine and covered with cellophane paper
After that, visible light illuminator (Kulzer, Translux) from above
Irradiate visible light for 30 seconds using
Cured. After that, the cured surface of the composite resin
Kuril Bar and Super Bond C & B (Sunmedical
(Manufactured by the same company) and bonded to prepare an adhesion test piece. Leave at room temperature for 30 minutes
Post-bonding test pieces are soaked in 37 ℃ water for 24 hours and then at 23 ℃.
After leaving it in the air for 10 minutes, at a temperature of 23 ° C, a strip with a speed of 2 mm / min
A tensile test was performed in each case to measure the adhesive force. After adhesion test
The fracture surface of each of these was destroyed by bovine teeth, and
Of interfacial destruction between the composite and the composite resin and dentin
It was either.

(II) Preparation of photo-curable composites resin: Triethylene glycol dimethacrylate 7.5 g, 1,3-
Bis (methacryloxyethoxy) benzene 7.5g, 2,2,4
15 g of an adduct of 1 mol of trimethylhexamethylenediamine diisocyanate and 2 mol of 2-hydroxyethyl methacrylate, 40 g of a composite filler synthesized by the method described below.
And fine powder silica RM-50 (manufactured by Nippon Aerosil Co., Ltd., fine powder silica) 30 g hydroquinone monomethyl ether 4 mg was kneaded with two rolls at 35 ° C. to prepare a composition. 10 g of this composition, and 45 mg of camphorquinone and 4
-45 mg of diethylaminobenzoic acid was thoroughly mixed with a spatula to prepare a photocurable composite resin.

(III) Production Example of Composite Filler A solution prepared by dissolving 0.1 g of benzoyl peroxide in 10 g of trimethacrylate of trimethylolpropane was placed in a mortar and pestle, and finely divided silica (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd., average particle size 16 mμ) ) Was added little by little and mixed. The mixture was hung on a small rubber roll when the viscosity gradually increased and became dull, and the amount of finely divided silica added was 9.5 g. Remove the obtained paste from the roll and press it at a mold temperature of 110 ℃ to 150 kg / cm ²
It was heat-cured at a pressure of ˜200 kg / cm ² for 10 minutes. The cured product was crushed with a ball mill to obtain 18.0 g of a composite filler that passed through a 230 mesh sieve. The average particle size of this composite filler was 11μ.

Example 1 8 g of methyl methacrylate (MMA), 1 g of 1,3-bis (methacryloxyethoxy) benzene (RDMA), 4-methacryloxyethoxycarbonylphthalic anhydride (4-META) 1
g, 0.1 g of polymethylmethacrylate (PMMA) and 2 mg of hydroquinone monomethyl ether (HQME) were mixed at room temperature to prepare a monomer mixture solution (A). 1 part by weight of a partial oxide of tri-n-butylboron (TBB.O) (manufactured by Sunmedical Co.) was mixed with 2 parts by weight of this (A) solution to prepare a dental adhesive composition, and this was prepared. The tooth was applied to a tooth with a small brush to prepare an adhesion test piece by the method described above. The results are shown in Table 1.
It was shown to.

Examples 2 to 4 and Comparative Examples 1 to 2 In Example 1, except that instead of using the monomers described in Example 1, the monomers described in Table 1 were used in the amounts shown in Table 1, An adhesion test piece was produced by the same method.
The results are shown in Table 1.

Examples 5-8, Comparative Example 3 In Example 1, instead of using the monomer described in Example 1, the monomer described in Table 1 was used in the amount described in Table 1, and no polymethylmethacrylate was used. A mixed solution (A) was prepared. Then the amount of TBB listed in Table 1
-Adhesion test pieces were prepared using this as a dental adhesive composition by mixing with O.

The results are shown in Table 1.

Comparative Example 4 HEMA 2.7 g, 2.6E 6.3 g, 4-META 1 g, BPO 0.1 g and HQME 2 mg were mixed at room temperature to prepare a monomer liquid (A). Then
A solution (B) composed of DEPT0.05g PTSNa0.2g and 99% ethanol 9.75g was synthesized, and (A) and (B) were mixed at an equal weight at room temperature to prepare a dental adhesive composition, which was applied to teeth. I applied it with a small brush. Then, an adhesion test piece was produced by the method described above. The results are shown in Table 1.

Example 9, Comparative Examples 5-6 Similar to Example 1 except that in Example 1, instead of using the monomers described in Example 1, the monomers described in Table 2 were used in the amounts shown in Table 2. An adhesive test piece was prepared by the method.
The results are shown in Table 2.

Claims (1)

[Claims] 1. A monofunctional (meth) acrylate monomer [A], a general formula [I] [In the formula, R ¹ represents a divalent aromatic residue having at least one aromatic ring and optionally having an oxygen atom or a sulfur atom in the molecule, and R ² and R ³ are respectively A hydrogen atom or a methyl group, and n and m are positive integers], [C] at least one (meth) acryloyloxyl group in one molecule. A dental adhesive composition comprising an acidic group-containing (meth) acrylate-based monomer and [D] trialkylboron or an oxide thereof.