JPH0759487B2 - 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 is also excellent in teeth such as enamel and dentin and dental alloys. The present invention relates to a dental adhesive composition having adhesive properties 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 (JP-A-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 liquid (meth) acrylic acid ester, amine, sulfinic acid (salt), and peroxide (JP-A-53-39331).
No.), MMA, 4-META, and tributylborane (TBB) have been reported (Nippon Toho, 28 , 452-478 (1985), etc. However, conventional adhesives and curable compositions have been reported. It was difficult to obtain sufficient adhesion to dentin, especially 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 adhesion performance, 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 study of a dental adhesive composition for tooth restoration, which has no adverse effects such as irritation to dental pulp, [A] monofunctional (meth) acrylate monomer, [B] specific Dental adhesive composition comprising a polyfunctional (meth) acrylate monomer having a urethane bond, [C] a specific acidic group-containing (meth) acrylate monomer and [D] trialkylboron or an oxide thereof Has found that the above object can be achieved, and arrived at the present invention.

[Means for Solving Problems] and [Action] According to the present invention, [A] a monofunctional (meth) acrylate-based monomer, [B] a polyfunctional compound having at least one urethane bond in one molecule. Functional (meth) acrylate-based monomer, [C] acidic group-containing (meth) acrylate-based monomer containing at least one (meth) acryloyloxyl group in one molecule, [D] trialkylboron or the A dental adhesive composition comprising an oxide is provided.

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-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, etc. Hydrocarbon group-containing (meth) acrylates of 2
-Hydroxyethyl (meth) acrylate, hydroxyl group-containing (meth) acrylate such as 2-hydroxypropyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monododecyl ether ( (Meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, and other ethylene glycol unit-containing (meth) acrylate, trifluoroethyl (meth) acrylate, per Fluorine-substituted (meth) acrylates such as fluorooctyl (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. The above can be mixed and used. Among these, alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth). ) A hydroxyl group-containing (meth) acrylate such as acrylate is preferable, and 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 having a urethane bond [B] used in the dental adhesive composition of the present invention is a polyfunctional (meth) acrylate monomer having at least one urethane bond in one molecule. The monomer is, for example, an adduct of 1 mol of a diisocyanate compound and 2 mol of a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate. As the diisocyanate compound, any of aliphatic, alicyclic and aromatic diisocyanates can be used, for example, hexamethylene diisocyanate, lysine diisocyanate,
2,2 (4), 4-trimethylhexamethylene diisocyanate, dicyclohexyldimethylmethane-p, p'-diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate , Naphthalene diisocyanate, and the like. More specifically, And the like.

Of these, aliphatic or alicyclic (meth) acrylates are preferable, and Is preferably used.

As the polyfunctional (meth) acrylate having these urethane bonds, a mixture of two or more kinds can 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 its acid anhydride.

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. The use of ethoxycarbonyl phthalic anhydride is preferable because it improves the adhesion to teeth, water resistance and the like.

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], and particularly preferably monofunctional When the functional (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, water resistance and durability are improved. In particular, the etching treatment for dentin is preferable because it exhibits 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 polyfunctional (meth) acrylate-based monomer [B]
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 in total.

Furthermore, the blending amount of the trialkylboron or its oxide [D] blended in the dental adhesive composition of the present invention is such that the monofunctional (meth) acrylate-based monomer [A] and the polyfunctional ( A total of 100 of (meth) acrylate-based monomer [B] and acidic group-containing (meth) acrylate-based monomer [C]
Usually 2 to 100 parts by weight, preferably 5
To 70 parts by weight, particularly preferably 5 to 50 parts by weight. When the trialkylboron or its oxide [D] is mixed with the above-mentioned (meth) acrylate-based monomers [A], [B], and [C], a polymerization reaction is initiated within a few seconds to a few tens of minutes. Therefore, the above [A], [B],
Separately stored with [C] and mixed immediately before use.

In addition to the above-mentioned essential components, other components such as a powdered inorganic filler, an organic polymer, and a polymerization inhibitor can be blended in the dental adhesive composition of the present invention as required. As the powdery inorganic filler, specifically, kaolin, talc, clay, calcium carbonate, silica, silica-alumina, alumina, titanium oxide, calcium phosphate, glass powder,
Examples thereof include 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.

[Advantages of the Invention] The dental adhesive composition of the present invention is excellent in low-temperature curability near room temperature and water-resistant adhesiveness, and is particularly mild etching such as tooth materials such as enamel and dentin and dental alloys. It has excellent adhesive performance for tooth treated with dentin and has non-irritating property to pulp, so it is a bonding agent for dental composite resin, hard resin, etc. It can be used as a dental adhesive composition. 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.

In addition, the method for evaluating the dental adhesive composition of the present invention and the production examples of the photocurable composites resin shown 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-Vidroxyethyl Methacrylate HPMA ・ ・ 2-Hydroxypropyl Methacrylate UDMA ・ ・ ・GUMM ...HEIP ...4-META ...4-MET ...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 EDT
Etching with A ・ 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, then cello with a 5 mm diameter hole
Hantape (approx. 13mm x 13mm) was put on. Example or ratio
Apply the bonding agent described in the comparative example to the circular hole and lightly
Teflon metal mold (direct
A cylinder with a diameter of 5 mm and a depth of 2 mm), and the photopolymerizable composite described below.
After filling with resin and covering the surface with cellophane paper,
On top of that, use a visible light irradiator (Kulzer, Translux)
And irradiate visible light for 30 seconds to cure the composite resin.
Let Then the cured surface of the composite resin and the acrylic
Le Bond and Super Bond C & B (Sun Medical Company
The adhesive test piece was prepared by adhering the same. After leaving at room temperature for 30 minutes
After soaking the adhesive test piece in 37 ° C water for 24 hours, empty it at a temperature of 23 ° C.
After leaving it in the air for 10 minutes, at a temperature of 23 ° C and a speed of 2 mm / min
A tensile test was conducted to measure the adhesive force. After adhesion test
All fracture surfaces were bovine tooth destruction and aggregation of composites resin.
No destruction or interface failure between composite resin and dentin
I was there.

(II) Preparation of photo-curable composite resin: Triethylene glycol methacrylate 7.5 g, 1,3-bis (methacryloxyethoxy) benzene 7.5 g, 2,2,4-
Trimethylhexamethylenediamine diisocyanate 1
15 g of an adduct of 2 mol of 2-hydroxyethyl methacrylate and 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) and hydroquinone monomethyl ether (4 mg) were kneaded at 35 ° C. with a two-roll mill 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. When the viscosity gradually increased and became dry and dry, the mixture was suspended in a small rubber roll, and fine silica powder was intermittently added to finally set the addition amount of fine silica powder to 9.5 g. Remove the obtained paste from the roll,
150kg / cm ² or 200kg / cm ² with a mold temperature of 110 ℃
It was heat-cured at a pressure of 10 minutes. The cured product is crushed with a ball mill and a composite filler that passes through a 230 mesh sieve is 18.0 g.
Got The average particle size of this composite filler was 11μ.

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

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
• A dental adhesive composition was mixed with O to prepare an adhesive test piece. The results are shown in Table 1.

Comparative example 4 HEMA2.7g, HEIP6.3g, 4-META1g, BPO0.1g, and HQME2mg were mixed at room temperature, and the monomer liquid (A) was produced. Then DE
A solution (B) consisting of PT0.05 g PTSNa 0.2 g and 99% ethanol 9.75 g was synthesized. (A) and (B) were mixed at an equal weight at room temperature to prepare a dental adhesive composition, which was applied to a tooth with a small brush and then lightly blown with air to volatilize ethanol. Then, an adhesion test piece was produced by the method described above. The results are shown in Table 1.

Example 9, Comparative Example 5 According to Example 8, the same tests were carried out using the monomers shown in Table 2. The results are shown in Table 2.

Claims (1)

[Claims] 1. A monofunctional (meth) acrylate-based monomer, [B] a polyfunctional (meth) acrylate-based monomer having at least one urethane bond in one molecule, and [C] one molecule. A dental adhesive composition comprising an acidic group-containing (meth) acrylate-based monomer containing at least one (meth) acryloyloxyl group therein, and [D] trialkylboron or an oxide thereof.