DE2446547A1 - ROENTGEN AND PERMEABLE FILLER FOR PLASTIC RESIN - Google Patents

Description

Lawyer file L 115

LEE PHARMACEUTICALS, South El-Monte, California, V.St.A.

Radiopaque filler for synthetic resin compounds

The invention relates to a radiopaque filler

for synthetic resin compounds, especially for dental and medical,

Repair materials.

In the manufacture of plastic ^! Materialize for dental © it is common to die of powdered glass or quartz as filler for the imrten benutztenHarzbindearittei to.

uer refractive index of FUlIstoffan unu d @ r refractive index of ausgehärtften conventional Aevyihfirzbiruleni & t on '' dl © in-diantaien and atälsinisuhen _ ·. Repair masses used vjgrdeß »sfed ^ injid homely, in the SröterarÄyrsg mn l _a 4S rock £» §§ <> ffegfe of such a maintenance stXMßfSissteriai-s aas ECiK8föt © ff

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50 911S / 12 24: ..

Dioxide glass as a filler and the curing of the acrylic resin binder a translucent repair is achieved. Such repairs will reflect the color of the adjacent tooth surfaces and blend nicely with the color of the restored tooth, especially if the repair is not too great.

Conventional repair materials containing silica glass there is a lack of radiopacity, which is necessary for the dentist to decalcify the repair material Tooth structure can differentiate between how it is present in the event of an injury caused by tooth decay, and how it has spread below the gums. To create radiopacity barium glass is sometimes used in place of conventional glass in such repair compositions. Barium glass, which has a refractive index in the desired range of 1.5 to 1.6 but has limited radiopacity and is often impermissibly soft and soluble in strong acids, so that repairs with such plastic containing barium glass do not reliably have a long service life and have a relatively low compressive strength. For example conventional acrylic resin repair compositions, which ordinary silicon dioxide or borosilicate glass as filler

hold, achieve a compressive strength of about 3164 kp / cm, while Barium glass repair course masses, which barium with a Refractive index contained in the range from about 1.5 to 1.6, rarely

2 if at all, achieve compressive strength values above 2109 kp / cm.

. The invention creates a tine material temperature for synthetic resin components, including total and medical repair materials, which are effectively impervious to _{9 has} a refractive index - see the refractive index of the hardened resin bond @ 1§ nlh @ Ft _s ynd it is treated aeirtslirJjgrer S§urefo @ st £ Mif3fc @ ut ν \ ηύ acceptable physical

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the production of mixed repair compounds for dental and medical purposes.

It has been shown that effective X-ray opacity is achieved when a small proportion (on the order of 10% to 35% by weight) of the filler material has a higher index of refraction than the remainder of the composition and that it is therefore not necessary that all of the filler in the repair compound be tightly adhered to the Refractive index of the cured binder is adapted. For example, a filler that contains 25% to 35% barium glass with higher Refractive index as the binder in the range of about 1.7 to about 2.0 while the remainder is conventional glass or borosilicate glass with an index of refraction that is the same as the index of refraction Approaching the cured binder not only creates an effective X-ray opacity, but also exhibits a transparency that differs from the pearlescent transparency of natural Teeth approaching. Such low proportions of barium glass with higher Refractive index has a minimal effect on the mechanical properties and acid resistance of the cured repair compound

Repair compounds that have a compressive strength in the range of

2 2

2812 kp / cm to 3164 kp / cm easily achieved.

The cured, radiopaque repair compounds of the invention in which highly radiopaque materials dispersed in a non-radiopaque medium X-ray images showing repair masses from normal To distinguish tooth structure and tooth injuries more effectively than conventional radiopaque materials in which the The filler consists essentially entirely of Bariura glass. the Particles with high barium glass content are exposed to X-rays from the rest of the filler particles and provide a contrast that is at least as good as that when in use a completely radiopaque barium glass with a Refractive index of about 1.5 to about 1.6 existing filler is achieved. The hardened repair masses according to the invention actually provide a greater contrast on the X-ray

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film than would be expected based on the relative proportion of high refractive index barium glass present, because the X-rays appear to be reflected or noticeably deflected by the discrete concentration of barium-containing material will.

The result is that an X-ray image of a Repair is not uniformly gray, but rather has a sparkling and grainy appearance. Due to the radiopaque repair compound, the tooth structure and massive metal fillings clearly produced different shades. The invention thus leads to x-ray images that can be more easily interpreted than x-ray images from repairs with known materials, and this result will be without loss of acid resistance and compressive strength achieved, which would result if barium glass with a lower refractive index were used as filler alone.

The difference between the appearance of X-ray images of repairs carried out with the composition according to the invention and X-ray images of repairs carried out with filled acrylic resin-type repair compounds which do not contain any radio-opaque material are readily accepted a comparison of FIGS. A and B can be seen. Fig. A shows a reproduction an X-ray image of a tooth, which is a repair compound the composition according to the invention contains. Fig. B shows a reproduction of an X-ray image of a tooth structure, the contains a repair carried out with an acrylic resin type compound, which does not contain barium glass or other radio-opaque material. Fig. C shows a reproduction of an X-ray image a tooth structure which contains a repair compound »which consists of metal amalgam, and it is readily apparent that it can also be easily distinguished from FIG.

Fillers according to the invention advantageously contain up to about 30 weight Percentage preferably £ twa 10 weight percent to about 30 weight percent, of a barium glass having a high refractive index of x about 1.7 to ETEA 2 _s 0 ₉ with the balance of substantially radiolucent filler materials, such as Silicon

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dioxide, quartz, glass, microfibrous hard-to-melt salts, such as calcium silicate or mixtures thereof or any other inert filler material is formed. Borosilicate glass is preferred. Both, i.e. the barium glass with the high refractive index and the remainder of the filler mass preferably have a particle size of about 0.5 µm to about 50 µm, with a average particle size from about 2 µm to about 15 µm.

The next to the barium glass with the refractive index from about 1.7 to about 2.0 components of the filler composition should be present closely approximate that of the cured resin binder in terms of their refractive index. In general, the refractive index of the hardened resin that of the essentially radiolucent FU11 material within about 0.005 refractive index units be adapted to differences of 0.01 refractive index units and even larger differences up to about 0.1 refractive index units are allowed in some cases. For example, if the refractive index of the cured resin binder is in of the order of magnitude of 1.53, the refractive index of the radiolucent filler material should therefore be as little as possible smaller than about 1.52 still larger than about 1.54. It should be noted, however, that there are some tooth stains with which a Radiopaque filler material having a refractive index value in the range of about 1.43 to about 1.63 in conjunction with a cured resin binder that has a refractive index on the order of about 1.53, can work together quite appropriately. In addition, it should be noted that materials with finer particle size narrower in terms of refractive index values must be adapted as larger particles. The smaller the particle, the more interfaces it provides for refraction with reference on the entire mass, which means that small differences in the refractive index are effectively amplified and for the unarmed Eye are more easily distinguishable than in the case of larger particles in the same mass.

The term "refractive index" used in the description in relation to powdery samples refers to the refractive index

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index, which is measured by a conventional test in which a measured amount of the powder in a number of mixed liquids whose refractive index is known in each case immersed, and it is determined the time "whereupon at which the powder _s disappears, the refractive indices of the resulting solutions measured and appropriate calculations carried out.

In connection with the fillers according to the invention, any synthetic resin binder can be used which is suitable for mixed dental and medical repair compositions. Currently available materials are mainly acrylic resins. Typical commercial products include the quartz-filled mixed dental restorative compound of the aliphatic diacrylate / aromatic diacrylate type sold by Johnson & Johnson, Inc. under the trademark "Adaptic"; the mixing repair mass of siliciumdioxidgefülltem aromatic / aliphatic acrylic Di at _s sold by the company Lee Pharmaceuticals under the trade name 'Prestige'; the unfilled aromatic / aliphatic diacrylate which is cured by ultraviolet light and is sold by the LD Caulk Co. under the trade name "Nuva Seal""* the commercial product" Concise "which is sold by the Minnesota Mining & Mfg. Co. which is essentially a quartz-filled product of the aromatic / aliphatic diacrylate type. Typical commercial resins are known, inter alia, from "Physical Properties and Finished Surface Texture of Composite Restorative Resins", Dennison et al., Journal of the American Dental Association, Volume 85, 101-108, 1972; "A Further Report on the Physical Properties of Five Composite Resins, Part II", GM Hollenback, Journal of Alabama Dental Association, Vol. 55, pp.17-23, 1971; "A Comparison of the Physical Properties of Four Restorative Resins, "Peterson et al. Journal of the American Dental Association, Vol. 73, pp. 1324-1336, 1966; and U.S. Patents 3,066,112, 3,179,623, 3,539,533, 3,730 947 and 3 751 399.

In dental and medical repair compounds, the fillers according to the invention are expediently from about 40% to about 90%, preferably

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preferably about 60% to about 85% of the total weight of the cured repair material.

The radiopaque filler mass according to the invention is has been described with particular reference to dental and medical repair compounds, but it is the same usable to any filled resin product or. Natural resin product To impart radiopacity. Articles formulated from polyethylene, polycarbonate, polypropylene or any other synthetic resin can therefore use the fillers of the invention Achievement of X-ray opacity included.

The preferred embodiments of the invention described below are merely representative embodiments. As part of the invention offers a number of further embodiments to the person skilled in the art.

Example I.

The radiopaque filler composition used in this example was a mixture of 60 parts by weight of radiopaque Borosilicate glass with a refractive index of 1.47 and 20 parts by weight of radiopaque barium glass with a refractive index of 1.93.

The size of the particles of borosilicate and barium glass has been reduced, by impacting the particles directly on each other and on a non-metallic surface in a stream of air at high velocity, the was used to avoid metal contamination. The particle size of the borosilicate glass and barium glass used ranged from about 0.5 µm to about 30 µm, the average being Particle size was about 2 µm. The borosilicate glass was "Corning 7740", which was purchased from Corning Glass Works. The barium glass was "Potters H-002" manufactured by Potter Industries, Carstadt, New Jersey, V.St.A.

80 parts dry weight of impermeable filler pulp were made combined with a polymerizable monomer mass, which consists of 10 Ge

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weight parts diglycidyl ether of ßis-phenol-Ä-dimethacrylate and 10 parts by weight of triethylene glycol dimethacrylate, catalyzed with 0.4 part by weight of benzoyl peroxide and 0.2 part by weight of N, N-dimethylpara-toluidine, duration.

The hardened repair compound was physical by the following Features marked.

Compressive strength 3094 kgf / cm ² Diametrical tensile strength 527 kp / cn Hardness, Rockwell H 114 _{Transparency quotient} (C 7n) 0.6

The test procedures used were essentially those which are given in the German patent application, file number P 24 37 378.2.

In addition, a disk of a sample with a diameter of 25.4 mm and a thickness of 3 _S 2 m _3, which was produced from the composition according to the invention, was tested for its acid insolubility, namely against samples with the same size and the same dimensions as were prepared from the commercial products "Concise" and "Adaptic" and cured according to the instructions given by the manufacturers in ate packs of the product sold for optimal curing. Each of the disk samples of the materials in question were then immersed in a 5 percent solution of dilute acetic acid for 120 hours. The composition according to the invention showed a weight loss of 0.5% at the end of the test. The "Concise" disk showed a weight loss of 0.58% and the "Adaptic" disk showed a weight loss of 1.41%.

The mass according to the invention was used as a filling material on bovine teeth tested in vitro and has been shown to give the tooth structure excellent X-ray contrast.

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Example II '

A mass with the following formulation was prepared and cured:

Diglycidyl ether of bis-phenol-A-

Dimethacrylate 16.0 parts by weight

Triethylene glycol dimethacrylate 8.0 parts by weight

Benzoyl peroxide. '0.3 "

N, N-bis (2-hydroxyethyT) toluidine 0.4

Amorphous silica (refractive index 1.55; particle size in the range from 0.5 µm to about 30 µm; average particle size about 2.0 µm) 56 _sec 0 "barium glass (refractive index 1.85; essentially the same particle size as the silica ). 20.0

After curing and the same test as for the product of Example I the following properties were determined:

Compressive strength 3 375 kp / cm ²

2 Diametral tensile strength 527 kgf / cm

Hardness, Rockwell H 113

Transparency quotient (C ^ _Q ) 0.52

Example III

Using the same formulations as in Example II and replacing the amorphous silica with the same number of parts by weight of quartz having the same particle size and refractive index, a class was obtained which, when tested in the same manner as the compositions of Examples I and II, had the following properties;

Compressive strength 2

Diametrical Tensile Strength 485

Hardness, Rockwell H
Transparency c

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Compared to the properties obtained with the compositions of Examples I ₁ II and III, samples having the same size and shape which and commercial from commercial "Adaptic""Concise" were prepared and the instructions of the manufacturer optimal according to obtain curing cured, tested for the same properties according to the same procedures. The following results were obtained for "Adaptic":

Compressive strength 2,391 kgf / cm ² Diametrical tensile strength 457 kg / cm ² Hardness, Rockwell H 103 Transparency quotient (C ™) 0.45

The following results were obtained for "Concise"

Compressive strength. Z

2 Diametral tensile strength 416 kgf / cm

Hardness, Rockwell H '101

Transparency quotient (Cj ₀ ). . Ο, ββ

In all cases, in vitro and in vivo tests have been considerable better X-ray opacity parameters with regard to repair compounds shown, made from "Adaptic" or "Concise" became"

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Claims (9)

- 11 claims: 1. X-ray opaque filler compound for synthetic resin compounds, characterized by about 5 weight percent to about 35 weight percent particulate barium glass having an index of refraction of about 1.7 to about 2.0 and through about 95 percent to about weight percent radiolucent particulate filler material with a refractive index, which is the refractive index closely approximates the synthetic resin mass to be filled. 2. Composition according to claim 1, characterized in that the FUlT material is selected from the group consisting of silica quartz, silica glass, and microfiber refractory Salting. 3. Composition according to claim 1 or 2, characterized in that the particle size the filler mass in the range of about 0.5 to about 50 µm and the average particle size is about 2 µm to is about 15 .mu.m, 4. Composition according to claim 3, characterized in that the particle size is in the range from about 0.5 .mu.m to about 30 .mu.m and the average particle size is about 2 µm. 5. mass, characterized by about 10 percent by weight to about 60 percent by weight of a polymerizable monomer and about 90 percent by weight to about 40 percent by weight of a filler plus small amounts on the order of two percent or less of conventional hardening additives, and characterized in that the filler is a combination from about 90 percent by weight to about 65 percent by weight of the filler of the powdered inert radiolucent filler having an index of refraction closely approximating that of the cured monomer; and from about 10 percent to about 35 percent by weight of the filler of a powdered radiopaque barium glass having an index of refraction in the range of is about 1.7 to about 2.0. 509816/1224 6. Composition according to claim 5, characterized in that the barium glass that the particle size has a refractive index of 1.9 of the filler about 0.5 µm to about 30 µm and the average Particle size is about 2 .mu.m that the polymerizable Monomer is a mixture of equal parts by weight of diglycidyl ether of bis-phenol-A-dimethacrylate and triethylene glycol dimethacrylate and that the powdered inert radiographic filler is a borosilicate glass. 7. Composition according to claim 6, characterized in that the pulverized Glass and the cured monomer have an index of refraction in the range of about 1.4 to about 1.6. 8. Composition according to claim 5, which is used as a dental repair compound is suitable, characterized in that it is used as the polymerizable monomer about 10 parts by weight of glycidyl ether of bis-phenol-A-dimethacrylate, about 10 parts by weight of triethylene glycol dimethacrylate, about 60 parts by weight of powdered borosilicate glass with a Contains a refractive index of about 1.47 and about 20 parts by weight of powdered barium glass having a refractive index of 1.9, the Borosilicate glass and the barium glass each have a particle size in the range from about 0.5 µm to about 30 µm and an average Particle size of about 2 µm. 9. Composition according to claim 5, which is used as a dental repair compound is suitable, characterized in that the polymerizable monomer is about 16 parts by weight of diglycidyl ether of bisphenol A dimethacrylate and about 8 parts by weight of triethylene glycol dimethacrylate contains that the filler contains about 56 parts by weight of amorphous silica with a refractive index of about 1.55 and about 20 parts by weight of barium glass with a refractive index of about 1.85, and that the particle size of the filler is in the range from about 0.5 µm to about 30 µm and the average particle size about 2 µm. 509816/1224 - "13 - 1Ö. Composition according to Claim 9, characterized in that the filler instead of about 56 parts by weight of amorphous silica about Contains 56 parts by weight of powdered quartz with a refractive index of about 1.55. 509816/1224