JPH0331684B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an adhesive that can firmly bond and fix a dental metal workpiece to a tooth, composite resin, resin core, etc. The dental metal workpieces referred to in the present invention include inlays,
onlays, crowns, bridges, denture bases, cores,
Refers to metal workpieces that are permanently or temporarily attached to the oral cavity, such as posts, pins, orthodontic appliances. In conventional dental treatment, when fixing these metal products to teeth, so-called luting cements such as zinc phosphate cement, carboxylate cement, and ionomer cement are used for bonding. However, these cements do not adhere to metals and teeth at all, or have extremely low adhesion strength, so a mechanical fit between the teeth and metal workpieces and these cements using unevenness is essential. be. Therefore, it is necessary to maintain the metal workpiece by cutting down even the healthy tooth tissue and applying a mechanical maintenance form such as an undercut. Also,
The cement gradually dissolves in saliva, resulting in serious problems such as metal workpieces falling off and secondary caries occurring. The present inventors have discovered that the current luting cement has
In order to solve these many problems all at once, we concluded that we should develop an adhesive that can firmly bond metal to teeth and is also water resistant. After intensive study, we found the following: We have arrived at the present invention. That is, the present invention provides adhesive properties expressed by the following general formula. [wherein, X: -O- or -NH-; Y:

【formula】

[Formula] -O-, -NHCO- Or -CONH-;

[expression] or

[Formula]; R ₁ : H or CH ₃ ; R ₂ : Hydrocarbon group having 2 to 10 carbon atoms and may be substituted with (m+n) valent halogen; m, n: 1 or 2, k: 0 or 1 ] and a curing agent consisting of an organic sulfinic acid salt (D), an amine or its salt (E), and a peroxide (F). Such adhesives exhibit strong adhesion to dental metals such as nickel-chromium alloys, cobalt-chromium alloys, gold alloys, stainless steel, etc., and to teeth, and the adhesive strength is extremely water resistant. . Preferably, a (meth)acrylic acid ester monomer (B) and a filler (C) having no acidic group are added to the adhesive of the present invention. The excellent adhesive strength of the adhesive of the present invention is achieved by the presence of the adhesive monomer (A), and examples of such monomers include the following. Furthermore, a group of compounds having a structure in which only the methacrylic part in the structure of the above compounds is replaced with acrylic can also be used. The common features of all of these compounds are a steric structural moiety in which another carboxyl group or hydroxyl group is located at a fixed position spatially adjacent to one carboxyl group, and a polymerizable doublet. It is at a point that has a bond. As a result of evaluating the adhesion of a large number of compounds to metals and teeth, the present inventors found that the above two conditions are molecular structural requirements for a certain compound to strongly adhere to metals and teeth. , arrived at the present invention. Among them

[Formula] Also teeth

The compound having the molecular structure of [Formula] had particularly excellent adhesive strength. Further, among the above-mentioned compounds, compounds having no amide bond in the molecule are preferable because they have excellent compatibility with the (meth)acrylate monomer (B) described below. In the present invention, the adhesive monomer (A) is preferably used as a mixture with the (meth)acrylate monomer (B), which is a copolymerization component. As such (meth)acrylate monomers, monomers having no acidic groups such as carboxylic acid, phosphoric acid, and sulfonic acid are usually used, and the following are exemplified. (i) Monofunctional (meth)acrylate Methyl (meth)acrylate, Ethyl (meth)acrylate
Acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)
Acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate (sometimes referred to as HEMA), 2-hydroxypropyl (meth)acrylate, dimethylaminoethyl ( meth)acrylate, diethylaminoethyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, 2,3-dibromopropyl (meth)acrylate (ii) Bifunctional (meth)acrylate Ethylene glycol di(meth)acrylate ,
diethylene glycol di(meth)acrylate,
Triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Acrylate, Propanediol di(meth)acrylate, Glycerin di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-
Pentanediol di(meth)acrylate, 1,
6-hexanediol di(meth)acrylate,
Neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, dibrome neopentyl glycol di(meth)acrylate, bisphenol-A di(meth)acrylate, 2,2-bis[(meth)acryloyloxy Polyethoxyphenyl〕propane〔 t = integer of 1 to 9], 2,2'-bis(4-acryloyloxypropoxyphenyl)propane,
2,2'-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (sometimes referred to as Bis-GMA), 1,2
-bis[3-(meth)acryloyloxy-2-
hydroxypropoxy]ethane, 1,4-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]butane (iii) 3-4 functional methacrylate trimethylolpropane tri(meth)acrylate, trimethylolethane tri( meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1, 3-diol]tetramethacrylate These monomers may be used singly or in combination,
Mixed with adhesive monomer (A). When selecting the monomer (B), consider the durability of the adhesive strength of the cured product, water absorption rate, mechanical strength, biological toxicity, and the viscosity of the monomer composition. A combination is determined. Generally speaking, preferred monomers are
Bis-GMA, 2,2-bis[methacryloyloxypolyethoxyphenyl]propane, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate Methacrylate monomers such as methacrylate, neopentyl glycol dimethacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, n-hexyl methacrylate, HEMA, and 2-hydroxypropyl methacrylate. Among these monomers, HEMA, 2-
For hydroxypropyl methacrylate and triethylene glycol dimethacrylate, if the proportion of monomers (A) + (B) exceeds 50% by weight, the water resistance of the cured product will deteriorate, so it is recommended to use it in a content range below this range. preferable. adhesive monomer
The content of (A) is in the range of 1 to 50% by weight, preferably 2 to 30% by weight based on (A)+(B). If it is less than 1%, the adhesive effect will be insufficient, and if it exceeds 50%, the carboxyl group of the adhesive monomer will reduce the water resistance of the cured adhesive. In the present invention, it is preferable that a filler is further added to the above monomer to form the adhesive. The addition of fillers significantly improves the adhesive's mechanical strength, adhesive strength and its water resistance. Furthermore, compared to adhesives made only of monomers, adhesives with an appropriate amount of filler added can have their fluidity, thixotropy, and tackiness appropriately controlled by appropriately changing the type and amount of filler added.
Ease of use (operability), which is an important factor in dental treatment, is greatly improved. Fillers that can be used in the present invention include natural minerals such as silica, quartz, feldspar, pottery stone, wollastonite, mica, clay, kaolin, and marble, silicon oxide, aluminum oxide, silicon titanide, boron carbide, and boron titanide. ceramics, water-insoluble inorganic salts such as barium sulfate and calcium carbonate, PMMA, polyvinyl chloride, nylon,
These include powders of organic polymer materials such as polystyrene (which may be amorphous, spherical, plate-like, or fibrous) or so-called organic-inorganic composite fillers that have recently been in the spotlight as dental materials. Among these, inorganic or organic-inorganic composite fillers are particularly preferred in the present invention. These fillers are used singly or in combination with the monomers mentioned above, but the inorganic fillers are usually γ-methacryloyloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichloride. Silane, vinyl tris (2
It is preferable to use a surface treated with a silane coupling agent such as -methoxyethoxysilane, vinyltriacetoxysilane, or γ-mercaptopropyltrimethoxysilane. monomer 100
By adding 20 to 500 parts by weight, preferably 50 to 400 parts by weight, of the filler to the weight part, significant improvements in the properties of the adhesive described above are observed. An initiator is added to the adhesive of the invention for immediate polymerization of the monomers at room temperature. A BPO-amine system is usually used for this type of purpose, but in the present invention, since the monomer (A) contains a carboxyl group, it is difficult to carry out immediate polymerization with this initiator system. As a result of investigating various initiators, the present inventors found that an initiator consisting of three components, an organic sulfinic acid salt (D), an amine or its salt (E), and a peroxide (F), is effective in polymerization curing and adhesion. It has been found that this method is particularly effective in expressing force. In the present invention, the organic sulfinic acid (D) may have any structure, but arylsulfinic acid is preferred from the viewpoint of storage stability. Cations that form salts include alkali metal ions, alkaline earth metal ions, ammonium ions, etc., and alkali metal ions and alkaline earth metal ions are superior in terms of storage stability and adhesive strength. Sulfinates include lithium benzenesulfinate, sodium benzenesulfinate, potassium benzenesulfinate, calcium benzenesulfinate, strontium benzenesulfinate, ammonium benzenesulfinate, and triethylammonium benzenesulfinate. , benzenesulfinic acid/N,N-dimethyl-p-toluidine salt, lithium P-toluenesulfinate, sodium P-toluenesulfinate, potassium P-toluenesulfinate, β-naphthalenesulfinate, styrene Among them, alkali metal salts of benzenesulfinic acid and P-toluenesulfinic acid are preferred. As the amine (E), a compound in which an amino group is bonded to an aryl group is effective, and the polymerization acceleration effect increases in the order of primary amine < secondary amine < tertiary amine. Preferred specific examples include N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,
N-diethanolaniline, N,N-diethanol-p-toluidine, N-methylaniline, N-
Examples include methyl-p-toluidine. Further, these amines may form salts with hydrochloric acid, acetic acid, phosphoric acid, etc. The peroxide (F) may be any peroxide commonly used as a polymerization initiator, but among them, benzoyl peroxide, m-toluyl peroxide, 2,4-dichlorobenzoyl peroxide, Diacyl peroxides such as octanoyl peroxide, lauroyl peroxide, and succinic acid peroxide are preferably used. Among these, benzoyl peroxide and m-toluyl peroxide are particularly preferred. Organic sulfinate (D) per 100 parts by weight of monomer
is 0.1 to 10 parts by weight (more preferably 0.3 to 5 parts by weight), amine or its salt (E) is 0.1 to 5 parts by weight, and peroxide (F) is 0.1 to 5 parts by weight (both are more preferably is preferably added within the range of 0.3 to 3 parts by weight). In addition to the above-mentioned essential components, the adhesive of the present invention may contain polymerization inhibitors, antioxidants, ultraviolet absorbers, various pigments, dyes, and phthalates, as necessary in accordance with various requirements for dental adhesives. Additives such as dibutyl acid, ethanol, and silicone oil as monomers
It can be added in an amount of 10 parts by weight or less, usually 5 parts by weight or less, per 100 parts by weight. In the adhesive of the present invention, the monomers (A) + (B) are used as the initiator (D).
When mixed with +(E) + (F), polymerization will start immediately, so (A), (B), (D), (E), and (F) should be properly separated and packaged until just before use. There is a need. For practical purposes, it is preferable to package the product in two parts, but in terms of storage stability, it is permissible to package the product in separate packages in which (A) and (D) are packaged separately, and (E) and (F) are also packaged separately. It is a system. Such packaging formats include (A+B+F)/(D+E), (A+B+
E)/(D+F), (B+D+E)/(A+F),
(B+D+F)/(A+E), (A+B+E)/
(A+B+F)/(D), (A+E)/(B+F)/
(D), (A+F)/(B+E)/(D), etc. Note that the filler (C) can be freely added to any of the above sachets. Among the above packaging formats, a particularly preferred one is a two-part packaging format in which (B) and (D) are also packaged separately (A+B+
F)/(D+E) and (A+B+E)/(D+F)
It is. The adhesive of the present invention is thus packaged separately and supplied to dentists, and when used, each package is mixed by the doctor's hands and polymerized and hardened to develop adhesive strength. In addition to the above-mentioned characteristics, strong adhesion to dental metals and teeth, and its water resistance, this adhesive also has the following characteristics:
Furthermore, it has the following characteristics. In other words, the combination of adhesive monomer (A) and initiator (D+E+F) results in anaerobic polymerization, so when a crown, inlay, etc. is bonded to a tooth, the adhesive filled in the gap between the tooth and these prostheses is Although it hardens quickly, excess adhesive that protrudes into the oral cavity is exposed to air and polymerization is significantly delayed. After the prosthesis has been bonded, the uncured excess adhesive can then be removed very easily. This significantly reduces the dentist's effort to remove excess adhesive after curing. Hereinafter, embodiments of the adhesive of the present invention will be specifically explained with reference to Examples. Examples 1-2 and Comparative Examples 1-5 As shown in Table 1, the structure of Z changed systematically.

Synthesize various monomers (A)′ of the formula
A liquid type adhesive was prepared, and its adhesive strength to human tooth dentin, bovine tooth enamel, and Ni-Cr alloy [Nauchrome (), manufactured by Towa Giken Co., Ltd.] was evaluated. (1) Preparation of adhesive: The powder-liquid composition is as follows. Agent (liquid): Bis-GMA 40 parts by weight 1,6-hexanediol dimethacrylate
30 〃 HEMA 23 〃 Monomer (A)′ 7 〃 Benzoyl peroxide 1.5 〃 Hydroquinone monomethyl ether
0.05 〃 Agent (powder): Silanized quartz powder 100 parts by weight Sodium benzenesulfinate 0.4 〃 N,N-diethanol-p-toluidine
0.4 To prepare the agent, spray a solution prepared by dissolving sodium benzenesulfinate and N,N-diethanol-p-toluidine in 10 parts by weight of methanol evenly onto quartz powder, and then evaporate the methanol. Ta. (2) Adhesion to dentin: The crown of a human molar was cut off with a cutter under water injection to expose the dentin. The dentin surface was acid-etched for 1 minute with a 40% orthophosphoric acid aqueous solution, washed with water, and then the moisture on the surface was blown off with an air gun. Next, a double-sided adhesive tape with a hole of 5 mm diameter was attached to the surface. Furthermore, the cross section of the human tooth was fixed so that it was horizontal, and a plastic ring with an inner diameter of 6 mmφ and a height of 5 mm was placed over the hole in the tape so that the centers of the holes coincided. Next, appropriate amounts of the agent and agent were kneaded at a weight ratio of 1:2 (about 1 minute) to form a soft paste.The mixture was press-fitted into the plastic ring, a hook for a tensile test was inserted, and the mixture was allowed to stand for 30 minutes. Thereafter, it was immersed and stored in water at 37°C. Note that bonded samples of 5 teeth were prepared for each adhesive. (3) Adhesion to bovine tooth enamel: The labial surface of the bovine anterior tooth was polished under water to create a smooth surface, and the same as with the dentin surface, phosphoric acid etching was performed, followed by bonding using the same method as human tooth dentin. I went. (4) Adhesion to Ni-Cr alloy: 10× with Nauchrome () (manufactured by Towa Giken Co., Ltd., Ni content 92%)
A flat plate of 10 x 3 mm and a round bar of 7 mmφ x 20 mm were cast, and each flat surface was polished with #1000 abrasive paper.
After washing with ultrasonic water and drying with an air gun, adhesive tape (Transpore) with a hole of 5 mmφ was pasted on the flat plate side. Next, the agents were mixed at a weight ratio of 1:2, and after about 1 minute, the resulting paste was applied thickly to the cross section of the round bar, and was pressed onto a flat plate to adhere. Leave it as it is for 30 minutes,
Thereafter, it was immersed in water at 37°C. In addition, 6 per adhesive
I made an adhesive sample of a book. (5) Measurement of tensile adhesive strength: After one week of immersion in water at 37°C, each sample was subjected to an Instron tensile tester.
Adhesive strength was measured at a crosshead speed of 2 mm/min. The average adhesive strength of 5 to 6 samples of each adhesive is listed in Table 1.

【table】

[Table] Examples 3 and 4 and Comparative Examples 6 and 7 Two paste adhesives (base and catalyst) were prepared with the compositions shown in Table 2, and the base and catalyst were mixed at a mixing ratio of 20:1 (weight ratio). Combined, the above
Ni-Cr alloy was bonded. Adhesion method is Example 1 and 2
is the same as After being immersed in water at 37°C for one week, the adhesive strength was measured. The results are listed in Table 2.

【table】

【table】

Claims (1)

[Claims] 1 (a) An adhesive monomer represented by the following general formula: [In the formula, X: -O- or -NH-; Y: [Formula] [Formula] -NHCO- or [Formula] or [Formula] or _{CH 3} ; , a hydrocarbon group that may be substituted with halogen; m, n: 1 or 2; k: 0 or 1] and (b) (i) a salt of an organic sulfinic acid, (ii) an amine or a salt thereof and (iii) dental adhesives comprising a hardening agent consisting of a peroxide. 2 The adhesive monomer is The dental adhesive according to claim 1. 3 The adhesive monomer is The dental adhesive according to claim 1. 4. The organic sulfinic acid salt of the curing agent is an arylsulfinic acid salt, the amine or its salt is a secondary or tertiary arylamine or a salt thereof, and the peroxide is a diacyl peroxide. A dental adhesive according to claim 1. 5. The dental adhesive according to claim 1, further comprising (c) a (meth)acrylic acid ester monomer having no acidic group. 6 The monomer is (a) component 1 to 50% by weight, (c) component 99 to
5. Dental adhesive according to claim 4, comprising 50% by weight. 7 In addition, (d) filler is added per 100 parts by weight of monomer.
The dental adhesive according to claim 1 or 4, wherein 20 to 500 parts by weight are added. 8. The dental adhesive according to claim 6, wherein the filler is an inorganic and/or organic-inorganic composite filler. 9. The dental adhesive according to claim 1, wherein the adhesive monomer and the organic sulfinic acid salt are packaged separately.