• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Compositions for use in dentistry which provide adhesion to dentin and enamel without the need for acid etching thereof, the compositions containing organic esters of phosphorus acids having chlorine or bromine bonded directly to phosphorus, and the organic radical of said esters containing at least one polymerizable functional group, and methods for using such compositions to repair or veneer dental tissue.
    公开号:SU1428177A3
    申请号:SU823394305
    申请日:1982-02-12
    公开日:1988-09-30
    发明作者:Эдвард Бункер Джемс
    申请人:Миннесота Майнинг Энд Мануфакчуринг Компани (Фирма)；
    IPC主号:
    专利说明:

    (21) 3394305 / 28-14
    (22) 12.02.82
    (31) 234560
    (32) 13.02.81
    (33) US
    (46) 09/30/88. Bul Number 36
    (71) Minnesota Mining and Manufacturing Company (US)
    (72) James Edward Bunker (US)
    (73) Minnesota Mining and Manufacturing Company (US)
    (53) 613.314 (088.8) (56) US Patent No. 4203220, cl. A 61 K 5/06, 1980.
    (54) COMPOSITION FOR DENTAL INSERTS (57U The invention relates to dentistry. The purpose of the invention is to increase adhesion. The composition is obtained in packages of one or many parts. Package inserts are prepared by combining one ester or several phosphoric esters with an activator, accelerator, inhibitor, and photosensitive catalyst. The mixture remains in its uncured state before irradiation. The multicomponent packaging of the composition for the tabs is obtained by combining a solvent, an activator and an accelerator in the first part, a phosphoric acid ester The notes and the catalyst in the second part. If both of the mix, the composition cures quickly. multi-component packaging provides ease of mixing, long shelf life and required physical properties after curing. Table 1.
    §

    to oo
    |

    The invention relates to medicine, namely therapeutic dentistry, and can be used in dental practice.
    The purpose of the invention is to increase adhesion.
    The composition for dental tabs contains a binder and an activator, where it contains a polymerizing ester of diglycidyl methacrylate ™ that bis-phenol and phosphorus oxychloride, phenyldichlorophosphonate, phenyldischlorophosphate, phosphorus trichloride, phosphorus pentochloride or phosphorus phosphorus, phosphorus trichloride, phosphorus trichloride, phosphorus trichloride, phosphorus trichloride; and sodium benzene sulphinate, potassium benzene sulphinate, ammonium benzene sulphate, sodium sulphite, potassium sulphite, ammonium sulphite, sodium sulphonate, potassium sulphonate or ammonium sulphonate, taken in quantitative ratios .% E:
    Binder 90.0-99.5
    Activator 0.5-10.0
    Phosphoric esters are used separately or in the form of adducts containing more than one phosphoric ester of the proposed composition. Phosphoric esters are obtained by combining phosphoric acid containing chlorine or bromine with a polymerizable monomer having at least one reactive 1a ionic hydroxyl group. When the polymerizable monomer has a high degree of initial viscosity, it is preferred to mix the phosphoric acid with the polymerizable monomer and a suitable diluent, for example triethylene glycol dimethacrylate.
    Phosphoric acid and the polymerizable monomer having at least one hydroxyl group react at a low temperature, e.g. at room temperature, and the viscosity of the reaction mixture increases, reaching an equilibrium state that is stable for a long time. In order to obtain good adhesive properties, the composition properties add a sufficient amount of phosphoric acid to the polymerized monomer.
     Polymerizing ester of diglycidyl methacrylate bis-phenol, other phosphoric acids, which can react with the polymerization MQHOMepaMH containing reactive hydroxyl groups, are used as a binder.
    five
    0
    0 5 0

    five
    0
    0
    five
    Examples include phosphorus oxychloride, phenyl dichlorophosphonate, phenyl dichlorophosphate, phosphorus trichloride, phosphorus pentachloride and phosphorus penta bromide. Such phosphoric acids can be used alone or in combination with one another. Phosphorus chlorine is the preferred phosphoric acid for use in preparing the phosphoric acid esters of the invention.
    Phosphoric acid and polymerizable monomers are mixed at room temperature and taken in an amount of 90.0-99.5.
    Adhesion strength, resistance to microdamages and other characteristics of phosphoric acid esters are assessed by preparing a polymerizable composition containing the proposed phosphoric acid esters together with the sulfur compound.
    Offered compositions usually contain sulfur, which is an activator, in amounts of 0.5-10% by weight. The activators are alkali metal salts, for example, potassium or sodium salts, or. ammonium salts, or anions containing sulfur, for example, anions of sulfate, sulfite or sulfonate. Sodium benzene sulphinate is the preferred activator.
    The composition typically contains a tertiary amine, which acts as a polymerization accelerator, in amounts of about 0.5-10.0 wt.%. Tertiary amines include DNRH - N, N-dimethyl-para-toluidine, N, K-bis (2-hydroxyethyl) - 3,5-xylidine.
    The composition for dental inserts contains a catalyst for polymerization, for example, peroxides, in particular benzoyl peroxide, acetyl peroxide, lauroyl peroxide and tert-butyl hydroperoxide. Benzoyl peroxide is the preferred catalyst. Photoinitiators can also be used (i.e. photosensitive catalysts), for example, mono-ketals from 1,2-diketones or a combination of benzyl and dialkylaminoacrylate or methacrylate.
    The composition may also contain auxiliary components, for example, solvents, stabilizers, fillers, pigments, inhibitors and other additives. Ethanol is the preferred solvent for use.
    in the composition. Quartz and glass, e.g. zinc glass, subjected to the necessary silane treatment, is the preferred filler for use in the composition. Asbestos-free talc is the preferred filler for use in the formulation.
    The composition of the present invention is obtained in packs of one part or a plurality of parts, for example, one-piece packings of inlays are obtained by combining one ester or several phosphoric esters with activators, an accelerator, an inhibitor and a photosensitive catalyst. The resulting mixture remains in a stable, uncured state until it is exposed to radiation. In addition, inlays are obtained with solid packages containing phosphate esters and a catalyst, but not containing activators or accelerators and bound to a layer of polymerized heating or composite composition. The resulting composition remains in a stable uncured state until it is combined with another component, such as an activator.
    Multicomponent packs of the composition for the tabs are obtained by combining a suitable solvent (for example, Zanol), an activator and accelerator in the first part and a phosphoric acid ester and a catalyst in the second part. As long as the packaging is not combined, it remains in a stable uncured state. If to mix both parts, then the resulting composition quickly cures. It is necessary to select the necessary
    the amount of each 1 $ omponenta to achieve the desired physical properties in the cured tab. You can also use combinations of phosphoric acid ester, activator, accelerator, and any auxiliary component. Multicomponent packaging of the composition provides ease of mixing, long shelf life and the necessary physical properties after curing.
    Multicomponent packaging of reducing compositional compositions are prepared, for example, with a combination of a polymerizable resin, for example, bisphenol ether diglycidyl methacrylate, an accelerator and a filler in the first
    parts and ester of phosphoric acid, catalyst and filler in the second part. Until it is combined, the resulting mixture remains in a stable uncured state. If you mix both parts, the resulting composition immediately hardens. It is necessary to select the amounts of each component in order to process and achieve the desired physical properties.
    The composition of the invention is applied similarly to known dental tabs. Dissection of the tooth cavity is simplified. Excavation is limited to the removal of damaged or defective tooth substance. Undercutting is usually not required, acid etching is also omitted. Therefore, the proposed composition reduces the time of dental treatment, reduces damage to a healthy dental substance.
    The invention is illustrated by the following examples.
    Example 1. Obtaining the organic ester of phosphorus oxychloride.
    10 g of phosphoric oxychloride are dissolved in a mixture of polymerizable monomer containing 95 g of bisphenol diglycidyl methacrylate ester of BIS-GMA, 2.0 g of benzoyl peroxide, 95 g of triethylene glycol dimethacrylate, 0.13 g of butylated hydroxytoluene, 0.34 g phenyl salicylate. and 0.24 g of glycidyl methacrylate. The resulting mixture is allowed to stand at room temperature for 5 days. During this time, the viscosity in the reaction mixture slowly increases from 200 to 1345 cP at 24 ° C. No further change in viscosity is observed after a further one. Infrared spectroscopy shows that the number of hydroxyl groups decreased. Infrared spectral analysis shows the presence of carbonyl, phenyl and phosphate groups. NRM spectroscopy indicates that the product contains a mixture of phosphate esters.
    The product of the described reaction is used as the first part of a two-component tab. The second part of this tab is a solution of 3 wt.% Sodium benzenesulfite and 1 wt.% DHPT in ethanol. The adherence of this tab with untreated dentin is evaluated using the following process.
    51428177
    4 bovine teeth of a specimen of bovine cattle of similar age and similar appearance are partially enclosed in round acrylic washers. Exposed f, this part of each tooth is ground parallel to the direction of the acrylic washer with a brush tool made of | 20-grit-silicone-carbide with a paper back side attached to the skin of the tooth washer to expose Dental dentin, during this and the following steps grinding and poly-d) teeth are constantly washed with water. Further grinding and polishing are performed by attaching a grinding agent from 400 grit-silicone-carnd with paper-backing and grinding to the stone washer.
    With a polished tooth surface, the ends of the dental wire are attached to the drawing jaws of the Jnstron apparatus, subjecting the connection of the insert to shear. At a slider speed of 5 mm / min, the average measured shear adhesion strength of the insert with dentine is 51 kg / cm. After standing in distilled water at 37 ° C for 42 hours (instead of 24 hours), the average adhesive bond strength with dentine is 60 kg / cm.
    Apply the proposed method, assess the adhesion strength of the tab with polished bovine enamel of a cattle specimen with or without acid pickling.
    Means of 600 grit aluminum with resist etching for one minute on the back side. 1 The teeth are then rinsed with distilled water using the equipment: Water Pik installed on the gesture for 15 seconds with the next air drying. One drop of each part of the two-component inset is inserted into the mixing pad. The drops are mixed with a spatula for 5 seconds, they paint the polished surface of the oaksJ and they are distributed in a thin film with compressed air. A prefabricated Teflon mold, having a 5 mm diameter hole, lined with a gelatinous sleeve, is placed around the tooth so that the main axis of the aperture in the mold is in the normal position relative to a polished surface grade orthophosphoric acid. Strength bonded to enamel, etched with a chelate etch, averaging 370 kg / cm and strength
    25 adhesion to non-etched enamel averages J20 kg / cm2,
    The tab is evaluated against resistance against intermittent thermal change. 6 samples of a tab on an etched dentine and 6 samples of a tab on an etched enamel, obtained by the proposed process, are subjected to a thermal change
    3g between 12 and 46 ° C for 500 periods. The values of adherence are then measured. After periodically changing the average adhesion strength of the insert with the non-etched dentin covered with the insert. The cavity is 40 kg / cm in thickness and others moderately are filled with a standard Concise denture. The mold in the tooth stands for 10 minutes at room temperature. Then gently remove
    The adhesion of the insert to the baseless enamel is 88 kg / cm. For comparison, Clearfil tabs are similarly rated
    the shape of the tooth, leaving the button-like image of the 45th. Initial average strength
    The Clearfil tab of the liner is 26 kg / cm with non-etched dent, 200 kg / cm with etched enamel and 50 kg / cm with non-etched enamel. After periodically thermally varying, the average bonded strength of the tabs of Clearfil is 13 kg / cm with a non-etched dentine of 21 kg / cm with a non-etched enamel.
    but a molded composition associated with a tab. The washer-tooth-tab combination is stored in distilled water for 24 hours. Coupling of a tab with polished-. In cattle, non-etched bovine dentin, cattle are evaluated by placing the washers with a tooth in the holder and fixing the holder in the cheeks of the Jnstron apparatus with the insert layer in a parallel direction relative to the direction of draft. A loop of dental wire (di-ai-ieTp 0.44 mm) is placed around the connecting button adjacent
    With a polished tooth surface, the ends of the dental wire are attached to the drawing jaws of the Jnstron apparatus, subjecting the connection of the insert to shear. At a slider speed of 5 mm / min, the average measured shear adhesion strength of the insert with dentine is 51 kg / cm. After standing in distilled water at 37 ° C for 42 hours (instead of 24 hours), the average adhesive bond strength with dentine is 60 kg / cm.
    Apply the proposed method, assess the adhesion strength of the tab with polished bovine enamel of a cattle specimen with or without acid pickling.
    percentage phosphoric acid. The strength of the bond with enamel subjected to acid etching is on average 370 kg / cm and its strength
    adhesion to enamel not etched averages J20 kg / cm2,
    The tab is evaluated against resistance against periodic thermal change. 6 samples of a tab on an etched dentine and 6 samples of a tab on an etched enamel, obtained by the proposed process, are subjected to a thermal change
    between 12 and 46 ° C for 500 periods. The values of adherence are then measured. After periodically varying, the average adhesion strength of the insert with the non-etched dentin is that the adhesiveness of the insert with the non-etched enamel is 88 kg / cm. For comparison, Clearfil tabs are also evaluated in a similar way. Initial average strength
    The adhesion of the Clearfil tab is 26 kg / cm with non-etched dentin, 200 kg / cm with etched enamel, and 50 kg / cm with non-etched enamel. After a periodic thermal change, the average bonding strength of the insert Clearfil is 13 kg / cm with non-etched dentine and 21 kg / cm with non-etched enamel.
    PR, and m e R 2. Storage stability. The composition of the invention described in Example 1 is stored for 4 weeks. When mixing and testing the composition after
    filtered and the filter cake washed with ether. The resulting red filtrate is concentrated to yield an oil weighing 60.5 g.
    5 g of this oil is added. 98.54 g of ethylacrylate triethylene glycol, 0.063 g of butylated oxytoluene, 0.2 1 bis-phenol Au, 1.2 g of benzoyl peroxide,
    The second component of the tab is a solution of 3 wt.% Sodium benzene sulphinate and 1 wt.% DHPT in ethanol. The composition was evaluated by the method of Example 1 and an average shear strength was obtained on an etched dentin of 5 kg / cm.
    Example 30, Example 1 is repeated.
    129, using 0.15 mol POCl, 0, ZOmol triethylamine and 0.30 mol 2-hydroxyethyl 1-methacrylate.
     The tab, obtained and evaluated by the method of Example 1, has an average shear strength on an untrained dentine 9 kg / cm.
    Example 31. The inlays of the invention described in Examples 1, 9, 16 and 19 are used as the base layer for the interlocking composition of the dental brackets. The resins are mixed and used on tooth enamel, which was previously polished with a BOO-grit-silica-binder grinding agent and contains polymerized zig-carbide with paper back side, washed with a Water Pik and air dried. Apply a layer of standard dental braces to the back of the dental braces and pads. A lining coated with an adhering agent is applied to the base layer and the resulting complex is cured for -10 min at room temperature. Cured. The kits are stored in water at 37 ° C for 24 hours and then evaluated against the average shear strength using Jnstron equipment. The results are shown below.
    40
    Editor M.Nedoluzhenko
    The ether of diglycidyl methacrylate of bisphenol and phosphorus oxychloride, phenyldichlorophosphonate, phenyldichlorophosphate, phosphorus trichloride, phosphorus pentachloride or phosphorus pentibromide, and sodium benzene sulfinate, potassium benzene as an activator. sulfinate, ammonium benzyl sulfinate, sodium sulfite, potassium sulfite, ammonium sulfite, sodium sulfonate, potassium sulfonate or ammonium sulfonate, taken in quantitative ratios, wt%:
    Binding 90.0-99.5 50 Activator0-10-10.0
    Compiled by S.Malyutina
    Tehred A. Kravchuk Proofreader L. Pilipenko
    The main layer of the average resin strength of the example on the cut kg / cm
    one
    88
    85
    sixteen
    91
    nineteen
    78
    15
     . 20
    25
    thirty
    For comparison, the standard Enamel Bond base layer of Concise 1960 glue is used instead of the base layers described. The average strength per cut is 31 kg / cm. Acid etching for 1 min with 37% orthophosphoric acid increases the average shear strength when using the base layer of Enamel Bond to 125 kg / cm.
    权利要求:
    Claims (1)
    [1]
    This example shows that the formulations of the present invention can be used as base layers in connection with a standard coupling material for dental brackets in order to achieve a high degree of moderate shear strength without the use of acid etching. Invention Formula
    A composition for dental inserts containing a binder and an activator, characterized in that, in order to increase adhesion, it is
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    引用文献:
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    GB8810411D0|1988-05-03|1988-06-08|Ici Plc|Adhesive compositions|
    EP0363903A3|1988-10-14|1991-03-20|Dentsply International|Adhesive containing pit and fissure sealants|
    US5525648A|1991-12-31|1996-06-11|Minnesota Mining And Manufacturing Company|Method for adhering to hard tissue|
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    US5849813A|1993-02-05|1998-12-15|Minnesota Mining And Manufacturing Company|Oxidative pretreatment for improved adhesion|
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    JPH10502343A|1994-06-30|1998-03-03|ミネソタマイニングアンドマニュファクチャリングカンパニー|How to join amalgam to the tooth surface|
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    JP2002544148A|1999-05-12|2002-12-24|デンツプライインターナショナルインコーポレーテッド|Sticky polymerizable monomers and dental / medical compositions therefrom|
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    法律状态:
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