DE2264103A1 - ADHAESIVE RESTORATIVE DENTAL MATERIALS - Google Patents

Description

DEN - 1

LEB PHARMACEUTICALS, South £ 1 Monte, CaI, / USA

"Adhesive res taurat ive dental materials ¹¹

The invention "relates to adhesive restorative dental compositions consisting of thermally curable aromatic and alicyclic polyacrylic resins as well as inorganic and organic, See fillers compose · Because of their adhesion, such restorative hats do not require the usual Cavity preparation; they will be without any odontomy used·

In dental technology, acrylate esters of bisphenolics were used Compounds used together with a wide variety of fillers as direct fillers · They were used in the Dental technology also used without fillers to close developing damage

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These resins can be either methacrylic acid or short chain in a smaller amount as reactive diluents contain aliphatic diacrylates. The reactive diluents are often added to the base batch to reduce the weight of inorganic reinforcing fillers to increase or to facilitate the penetration of unfilled systems into the developing damage

In preparing these direct filler materials, the amount of filler used is a satisfactory one clinical behavior critical. The fillers are used in weighting volumes from 70 to 85 pounds and are used to reduce polymerization shrinkage and thermal expansion. This is important for a satisfactory fieteneion of the masses in the usual retensive cavity preparations.

This high, commonly used filler concentration gives satisfactory compositions for use in conventional retensive cavity preparations. Because of their paste-like consistency, however, these masses have a. poor flow behavior and consolidate prepared adamantine and dentine surfaces less well than unfilled systems. Besides that make the poor flow properties the achievement of smooth, even connections between the masses and of the dentin or adamantine difficult so it in general it is necessary to process the masses considerably after hardening with dental instruments and to smooth them.

Restorative systems based on unfilled poly-

methyl methacrylate have good flow behavior and a good consolidation of adamantine and result in equal-

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massive connections, but they have to be in order to get optimal results can be achieved with time-consuming techniques, to keep the polymerization shrinkage low. When polymerized beads of methyl methacrylate are used as fillers were used, it turned out that the masses did not flow well and did not wet each other well Materials still unfilled polymethylene methacrylate of the booth The technique that was particularly suitable for certain non-surgical restorative procedures continued to become the conventional Cavity preparations used.

So far the use of more or less lightly filled diacrylates or polymethyl methacrylate systems has been used Avoided because of the unfavorable influence on the strength properties. Furthermore, it was found that in such In lightly filled systems, the filler settled during shipping and storage in the dental shop. The suspension of the fillers was extremely difficult and time consuming. Furthermore prevented the presence of the fillers the realization of good flow properties and disrupted the wetting and surface consolidation of prepared teeth, which is necessary for long retention in the dog.

Until now, needles, fibers and cotton wool, which were primarily but not exclusively made of glass, were only mixed used with particulate and / or spherical fillers. Obviously, the very heavy weights that were required for the masses could be that in usual Cavity preparations should not be used can easily be achieved with reinforcements consisting predominantly of fibers, since the viscosity with the fiber used

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Beschverungsvervichten cannot be reconciled
could. The highest strengths in clinically usable systems could only be achieved with a combination of fillers and not with the exclusive use of fiber reinforcement.

A number of systems have shown improved adhesion to dentin and adamantine, but this adhesion has gradually been lost under the wet conditions in the customer. Some of the best values reported in the literature have been made with
special polyurethane systems, apparently because the isocyanate component of the approach removes surface water, which would adversely affect the chemical bond. Improved bonds have also been achieved with special catalysts for acrylic resins, the
also react with the surface water. It was
showed that a greater penetration with unfilled polymethyl methacrylate than with the filled composite
restorative masses was achieved. A greater surface consolidation of the adamantine and dentine is achieved through
the tongue-like projections of the resin reached into the spaces created by the etchant used in the preparation of the surface. Such protrusions are not easily broken by moisture, as is often the case with chemical bonds.

According to the invention, a new adhesive dental compound is now proposed which is based on filler fibers ("fiber wadding ¹ ') with a certain size, these filler fibers being suspended in a liquid polyacrylate resin mixture with a viscosity of less than 5000 centipoiee. The special fibers used make 30 to 70 wt -.%

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the entire crowd. The compositions according to the invention show unusual adhesion to etched adamantine and dentine.

With the masses according to the invention, calibrating Adamantine damage, hypocalcific lesions, and ablated and abraded edamantine or dentine can be repaired without that the usual cavity preparations and the resulting resulting damage to healthy tooth parts must be carried out. When these new masses are correctly applied then they can be coated without any operational measures of discolored aamantine or to mask other restorative materials, such as unsightly ones Amalgam fillings.

It has been found that the difficulties previously encountered are due to the use of a special fiber reinforcement in thermosetting diacrylate resins with a viscosity of less than 5000 centipoise can be overcome · Bei excellent suspension can be achieved with such diacrylate resins or diacrylate resin mixtures. If the special If fillers are used in certain loading weights, then they result in surprisingly improved results Strength properties, in particular high compressive strengths as well as high hardness and high edge strength. If the fiber fillers are used with weights, these properties are desirable are obtained, then the adhesive compositions show excellent flow behavior, which is at least partially for the extraordinary consolidation of prepared dantin and adamentino surfaces is responsible.

The adhesive restorative dental compositions according to the invention

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have a unique combination of strength, relatively low polymerization shrinkage, excellent shelf life, and in particular the filler in good distribution remains, excellent flowability, excellent wettability of adamantine and sentin and Exceptional adhesion, which does not deteriorate even if the mass is exposed to the water in the mouth.

The adhesive compositions according to the invention show similar ones Bung-like projections such as those obtained with unfilled polymethyl methacrylate. It is believed that the Fiber reinforcements with the weight weights used do not so much affect the gaps in the adamantine and dentine block, as is the case with particulate fillers at the same loading weight. Besides that saturate and fill the diacrylate systems, which are used in the compositions according to the invention, the spaces easy. The overall effect of this surface consolidation results in higher mechanical interlocking and thus higher Adhesive strengths than found in the known compositions. Some of the fibers will be during of the application in such a way that they protrude to a certain extent into the prepared adamantine or dentine damage, so that they act as an additional mechanical holder act against shear forces, so that the entire interlocking between the hardened mass and the substrate is improved will.

Such mechanical adhesion is less prone to break in the mouth than chemical bonds between which adamantine and dentine and the mass are present · The adhesive strength obtained depends less on

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the chemical nature of the surface on which also a absorbed monolayer of water and fluorine-containing particles can be present

The fibers or batts used as fillers in the adhesive composition according to the invention, have a length of 1 to 10Ou. and a diameter which ranges on average from 1/20 to 1/5 the length of the fibers. In general, any fiber material is more organic or inorganic nature with the appropriate dimensions for the reinforcement of the diacrylate matrix, provided that that the reinforcement material gives the cured cash register an acceptable appearance. Within this expanse Borders, some materials are preferred over others. For example, quartz needles and fibers can be used but it has been proven to be more beneficial to use fibers with a hardness on the Mohs scale of approximately 3.5 to about 6, as these fibers give the cured register a better polishing ability than the harder ones Fibers. Sapphire fibers can be used, but they are very expensive and less useful as a whole cheaper fibers such as calorie silicate fibers. Organic fibers are inherently expensive to manufacture in the desired shape. While they give an acceptable appearance and improved polishability, they do not give equivalent Reducing the thermal expansion of the cured hasse, as is the case with inorganic fibers, and they are also generally stronger in customer fluids soluble than the inorganic fibers, so in general inorganic fibers are preferred, and it has been found that calcium silicate fibers are particularly suitable. As used herein, the term "fibers" includes

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226A103

Materials that are commonly used as tapes, needles or Wadding, provided that they have the specified dimensions.

The respective fiber weighting of the mass depends on the original viscosity of the resin mass and the desired flow properties. For resins with a low initial viscosity, higher fiber weights can be used, and conversely, for resins with higher initial viscosities, lower fiber weights should be used. In general, the exact weight weight will be determined by the flow properties of the finished composition. It should be chosen so that the tongue-like projections in the etched adamantine are at least 20 Ji long.

Accelerators and analyzers are also included in the cash register incorporated for the resin, so that appropriate setting and curing times are achieved. Gel times from 1 to 2 Minutes and curing times of 1 to 5 minutes are generally suitable. Amine accelerators and peroxide catalysts are preferred. '. -

As already mentioned, the adhesive restorative dental materials according to the invention enable the repair of removed adamantine and dentine, especially in the case of gingival erosion, without the time-consuming classic surgical preparations have to be carried out. Ss is only necessary, the adamantine or dentine with a pretreat a suitable etchant, e.g. with an inorganic acid, e.g. phosphoric acid or hydrochloric acid, or an organic acid, for example lemon

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acid. The etchant removes deposits and food residues and conditions the substrate in such a way that it can be wetted more easily and the tongue-like protrusions of the adhesive Hate picking up easier.

It is very important that the surface to be treated is carefully checked before the adhesive compositions according to the invention are applied is dried.

A greater adhesive strength is achieved if afterwards to the application of the etchant the tooth is treated with an anchoring agent, although this is successful Application of the adhesive composition according to the invention is not required. It's too. recommend that the Pulp fibers are treated with an anchoring agent before being incorporated into the mass. Such anchoring means are known in the art. examples for this are Silanes with functional organic groups. It has been found that particularly good results are obtained when the tooth is treated with a silane in which the functional organic G group consists of a hydroxyl group. Preferably, the silane agent for treating the fibers has one functional acrylic group.

As already mentioned, the adhesive restorative mass according to the invention consists of a suspension of a fiber filler, wherein the pasers have a length of 1 to 100 ^ i and a diameter have an average of 1/20 to 1/5 of the Paser length, in a diacrylate resin or resin mixture, the one Has an initial viscosity of less than 5000 centipoise » and wherein the fibers constitute from 30 to 70 weight percent of the composition. The fibers preferably make up 40 to 70 wt .- #, in particular 55 wt .- ^, from.

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In general, all organic and inorganic fibers with the above dimensions can be used, but inorganic fibers with a Mohs scale hardness of As already mentioned, 3.5 to 6.0 are preferred · Particularly calcium silicate fibers are preferred. A commercial mix of calcium silicate fibers that worked very well has an average fiber length of 5.5 u, 97 wt .- # of the fibers less than 20 η and 94 wt .- ^ are less than 10u long, the diameter being borrowed 1/15 to 1/13 of the length.

The resin component of the composition according to the invention preferably consists from a mixture of 25 to 90 wt .- ^ of a compound of the formula

O O

Ii ..Il

CH ₂ = C - CO - jra? - C - C = C9 ₂ - I

R ₁ A ₁

wherein R _{1 is} hydrogen or alkyl having 1 to 4 carbon atoms, preferably hydrogen or methyl, in particular methyl; and
R stands for the following:

a) (CH CH-O) _x , where χ is an integer from 1 to

^R. ₂

5, preferably 3 »and R _{2 is} hydrogen or alkyl having 1 to 4 carbon atoms, preferably hydrogen;

b) CH ₂ (CH ₂ ) CH ₂ O, where y is an integer of 1 or 2;

OH OH

c) -CH ₂ CH-CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ Ch-CH ₂ O-; or

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d) -CH ₂ -CH-CH ₂ O-WOrIn IL · for -OH or -0-CC = CH

i, ■ Oi ₁ ._

represents and R. has the same meaning as above;

and 10 to 75 percent by weight, preferably 30 to 70 percent by weight, one aromatic or alicyclic polyacrylate compound with which Limitation that the viscosity of the mixture is less than 5000 centipoise. Have the preferred resin blends excellent handling properties, very satisfactory gel and curing times, high compressive and flexural strengths, low shrinkage on curing and low coefficients of thermal expansion. In addition, they have a ( relatively low water adsorption. Particularly preferred compounds of the formula I are dimethacrylates among the above Letters a) and especially triethylene glycol dimethacrylate.

It is preferred that the aromatic polyacrylate be at least Contains 2 aromatic rings in the structure, and it is further preferred that the alicyclic polyacrylate be at least has two alicyclic rings in the structure. The preferred diaromatic polyacrylates include BIS-GKA or Bisphenol-A-bis- (3-methacrylato-2-hydroxypropyl) -ether or the dimethacrylate, which is different from the ethylene or propylene oxide adduct derived from bisphenol-A.

A preferred dialicyclic compound is dimethacrylate, which is derived from hydrogenated bisphenol.

The most preferred component used in admixture with the compounds of formula I is bisphenol-A-bis (3-methacrylato-2-hydroxypropyl) ether.

A particularly preferred composition according to the invention consists of

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a suspension of calcium silicate fibers in a resin mixture from about 60 parts by weight of bisphenol A >> bis (3-methacrylato-2-hydroxypropyl) ether and 40 parts by weight of triethylene glycol dimethacrylate, wherein the fibers are approximately 55% by weight of the mass turn off.

Representative for aromatic and alicyclic polyacrylates, used according to the invention besides those mentioned above are connections like:

X O I Il

.CH

CH = C-C = C

² ι ■

^x i

n. - cECl ·: .- - c- c- ο ch

wherein X and X. each independently represent hydrogen, lower Alkyl, i.e. straight or branched alkyl of 1 to 4 carbon atoms, preferably methyl, or halogen, preferably Chlorine, with a preferred example of a compound of Formula 11 being the following:

CH, I "

CK ₂ = C- C- O- CO ₂ CHCH ₉ - ΟΙ ί ■ "· OO

CH-

CH,

CH ₂

- C = O

O— ^ ■ - v ^ -

~ ^J 2

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which also as bisphenol-A-bis- (2,3-dimethacrylatopropyl-ether) can be designated; and

Il

₂ CK

OH

C X

where X is hydrogen, lower alkyl, i.e. straight or branched alkyl having 1 to 4 carbon atoms, preferably methyl, or halogen, preferably chlorine (X = methyl is very particularly preferred), a preferred example of a compound of the formula III being the following:

O U

CH CH

· OH.

CK-CHCH-CCO = CH, • ² J ² \ - OH-. '. · 0

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The acrylates of the formula II can be prepared by mixing BIS-GMA with an excess of acrylic chloride in Presence of a tertiary amine, such as triethylamine or Pyridine.

The compounds of the formula III can be prepared by using the triglycidyl ether of trihydroxybipbenyl with kethacrylic acid in the presence of a catalyst, e.g. a tertiary amine, triphenylphosphine or triphenylantimony, implements.

Compounds of the formula can also be used:

Il ι '

■ NTT _ <-> / -> / "> ΛιΤΤ.

'I.

wherein X., X- and X, for hydrogen or lower alkyl groups, which preferably have 4 or fewer carbon atoms. Preferred compounds of the formula IV are bisphenol A bis (2-methacrylatoethyl) ether of the following formula:

-H ₃

. . CH ₃

and Biephenol-P-bis- (2-methacrylatopropyl) -ether of the formula:

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H, CH ₃ . _ ν ;, ..- · _ .CH ₅ CH ₃

The diacrylates of the formula IV can be prepared by two processes will. The first method is that you mix an acrylic chloride with a corresponding bisalcohol compound according to the following reaction:

2 CH ₂ = C -C-CL + KC-X ₄ -OH

\ * ■ ι ·

CH ^ = CCOX ₄ -OCC = CH + 2HCl

■ ■ ^s H. ⁴ .11 ² ..

O O

in this reaction a base can be used, to remove the hydrogen chloride formed. The base can, for example, be a tertiary amine such as triethylamine or Pyridine. On the other hand, the bis-alcohol could be reacted beforehand with a base, for example its disodium salt produce, which in turn could then be reacted with the acid chloride.

The second process for the preparation of the diacrylates of the formula

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IV consists in the transesterification of the corresponding bisalcohol with lower alkyl esters of acrylic acids according to the following Reaction:

Xo

! ■

2 CH, = C-CCX. + HC-X ^ ₁ - CH

Any lower alkyl ester can be used in this process. In practice, X ₁ - but preferably a methyl group, as these methyl esters are more accessible and the methyl alcohol obtained as a by-product is the most volatile *

Further polyacrylates that can be used according to the invention are compounds of the following formulas:

O-C-C = CH,

Ul "

CX

^ I l | ■. "I XC- ■ CH

C X

HO

K O

CH-CH-O-C-C = CH ₀

Ii ι ■ "

O X

YJI

wherein in each of formulas V to VII, X is hydrogen, lower alkyl or halogen. In the above formulas V to VII , the preferred meaning for X is methyl.

Of the compounds of the general formulas V to VII which can be used according to the invention, three compounds are particularly preferred, namely:

CHL = C -

-C = CH

which is bis (3-methacrylato-2 ~ hydroxycyclopentyl) ether acts;

C- C-CH, -CHCH - 1 ² O CH

- CH, - CH-CH, - C- C- C = CH.,

OH

O CH,

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-is-

which is 1,3-bis (3-yneethacrylato-2-hydroxypropoxy) benzene acts; and

HO

CH ₉ = C - CO-

² 1 H

CH O

CH-CH ₀ -OCC = CH.

ι ² ι) ι -

OH

O CH.

which is 1- (2-methacrylato-1-hydroxyethyl) -3-hydroxy-4-methacrylatocyclohexane acts.

Other representative compounds have the formula;

Il

CH ₀ = CC-OXO-CC = CH ₀

VIII

where X is

CH,

ι ■

CH

(iii)

ouch

■ (iv)
or

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and X. is hydrogen, lower AlKyI or halogen stands.

In the own formula VIII, the preferred meaning is for X. methyl. Group (i) ″ is also preferred for X. For this reason the connection will be:

■ ν ° Λ ■ CH ₃
~ \ I / Λ 9 C = CH
ι ^ _ CH ₂ -, ^ - ^ ¹ - \ / -, / \ - Π- Γ ¹ - OH ₃ . ν ι ν_ J CH ₃

VILIa

the name 2,2-bis- (4-methacrylatocyclohexyl) -propane is most "preferred as a compound of the formula VIII.

The compounds of the formula VIII can by reacting an acrylic chloride or a derivative thereof with the corresponding Diol by methods well known in the art be asked. The reaction is generally carried out in the presence of a tertiary amine such as triethylamine or pyridine as Carried out acceptor for the hydrogen chloride generated in the reaction.

All of the compounds defined by Formula I are with Except for dirnethacrylate or diacrylate of diglycidyl ether

in trade

from butanediol / available. The latter can easily be done by professionals be prepared, for example by reacting an acrylic acid or Kethacry1äure with the diglycidyl ether of Eutanediol.

3 O 9 fi 2 8/1 Q 7 U

Appropriate catalysts and accelerators will be found in the cash registers added so that optimal gel times between 60 and 120 Seconds and optimal curing times between 90 and 240 seconds can be obtained. This ensures that the cash flow is sufficient to allow the necessary protrusions into the adamantine arise while at the same time achieving reasonable times during which the patient sits in the chair. Ss For example, under some clinical conditions, slightly shorter curing times may be desirable, such as e.g. if only single small lesions of hypocalcitated Adamantine, or that slightly longer setting times are beneficial when treating gingival erosion over a full quadrant of the tooth. Pure this Applications that cure between about 40 seconds and about 5 minutes may be desirable.

The catalyst and accelerator can be incorporated into separate parts of the resin, which are then immediately prior to use the application, or the catalyst can be added to the " Filler can be added, in which case the dry coated filler is added to the accelerated resin shortly before application is added, or a catalyzed layer can be applied to the dental substrate and then with an accelerated Layer are covered, the mixing taking place in situ and wherein the excess material is wiped off. the The latter technique is particularly suitable for filling developing holes and cracks on the occlusal surfaces of adult teeth. This two-fluid system is particularly suitable for non-surgical repair gingival erosion, and the dry filler and liquid system is particularly suitable when

2 0 9 8 7 Η I 1 0 7 n

especially long shelf life is desirable before use or if the material is to be stored in warmer areas without cooling.

As already mentioned, the resin compositions according to the invention cured by adding an activator or accelerator and a catalyst.

The type of accelerator depends on the resin compound used and the desired processing time. In general, accelerators can be used in amounts of from 0.001 to 5% by weight, based on the monomeric resins used. The Kenge the accelerator is located in most cases between about 0.5 to 2 Grew.-f ", based on the monomers used resins, with about 1.5 wt - '/> are generally preferred.. Examples of accelerators that have been used are Ν, ϊί-dimethyl-p-toluidine, p-toluenesulfinic acid, N-bis- (hydroxyethyl) -p-toluidine, and other tertiary amines well known in the art. "^ The preferred accelerator is N-bis (hydroxyethyl) ptoluidine.

Although peroxide catalysts, such as benzoyl pero: -; id, are preferred, however, other catalysts known in the art can also be used.

Catalysts are typically used in amounts of from about 0.2 to about 2 percent by weight based on the monomeric resins. In general, amounts from 0.50 to 1.0 wt .- ^, based on the monomeric resins, satisfactory. In the pail in which the catalyzed component is layered on the surface of the tooth in front of which contained the accelerator-

3 0 9 & <? R / 1 0 7 U

the component is applied, the catalyst in higher concentrations, such as about 5 to 8 wt .- ^, be used.

As is well known in the art, small Kengen dyes or particulate pigments can be added to the mixtures can be added to achieve shades that are closer to the natural shades of the individual teeth. tuck can, as in the case of pigments, be incorporated into the resin component or dry component of the mass by the manufacturer or they can be supplied separately in a form added by the dentist during mixing will. For example, know up to 10 wt .- ^, based on de Resin component, titanium dioxide added as a matting agent to mask discoloration in the adamantine or amalgam seals.

The cash register can also contain smaller amounts of common components, which are used in the art, such as polymerization inhibitors, for example 25 to 100 ppm hydroquinone, and U.V. stabilizers and antioxidants, for example 3-tert-butyl-4-diethylphenol and butylated hydroxytoluene in denominations of 0.01 to 5% by weight, based on the resin.

The best results are obtained when the inorganic filler is treated with an anchoring agent, such as is well known in the art. Such gowns improve the bond between the organic polymer binder and the surfaces of the fiber fillers and maintain the initial strength properties in the oral environment. Anchoring means, which have proven to be particularly suitable are the ethylenically unsaturated organosilane anchors

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funds. The fiber filler can be treated with the anchoring agent, for example, in the manner described in US Pat. No. 3,066,112, an aqueous solution of tris (2-methoxyethoxy) vinylsilane being catalyzed with sodium hydroxide so that a pH of 9.3 to 9.8 is formed, and the filler is treated with the solution, for example with 1/2 fi of silane, based on the weight of molten quartz. A slurry prepared in this way is dried at about 125 ° C. and cooled. Alternatively and preferably, the fibers are treated with a hydrolyzed neutral silane solution in dry ether, as described below.

The duration of the etching pretreatment depends on the particular etchant used and the condition of the tooth. In general, the length of the pre-treatment also depends on the acid used and the nature of the tooth. For example, milk teeth and younger permanent teeth typically require less treatment time than older permanent teeth. Teeth that have been treated with fluoride may require longer etching times than those that have not been treated in this way. It has been found that an etch of, for example, 2 minutes with 50% phosphoric acid is generally satisfactory for adult adamantine. Essentially similar results are obtained when etching with 85% phosphoric acid for 1 minute. The etching treatment can easily be adapted by the dentist to the respective situation.

To further improve the adhesion to the tooth substrate, a primer or anchoring agent can be added to the Etching treatment can be applied to the tooth. Suitable

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Primers are the silanes with functional organic Groups such as those above for the treatment of fiber fillers · Other anchor means well known in the art and which can be used are the reaction product of glycidyl methacrylate and N-phenylglycine as well as glycerophosphoric acid dimethacrylate etc.

Surprisingly, it has been found that excellent results are obtained when a silane with a functional Epoxy group is used as a primer for the composition containing acrylate resins, whereas the teachings and US Pat Experience of the prior art indicates that the functional organic groups of the silane match those of the Resin component should correspond.

In the following examples the calcium silicate fibers used are with a silane anchoring agent as follows pretreated.

A mixture of 100 g of gamma-methacryloxypropyltrimethoxysilane and 100 g of water is acidified with acetic acid to a pH of 3 and stirred at room temperature until the system has become homogeneous. The aqueous solution is extracted with 100 g of ethyl ether and the aqueous phase is discarded. The solution contains 4.6 g of hydrolyzed silane per 10 ml of solution. A sufficient amount of this solution is added to the calcium silicate filler so that 1.2 wt -.% Hydrolyzed silane be applied to the filler. The solution is then added very slowly with stirring so that thorough mashing is obtained. The ether solvent evaporates very quickly.

A particularly useful anchoring agent for the foundation

0 9 8 2 8/1 0 7 n

tion of the tooth surface to be treated is hydrolyzed gamma-glycidoxypropyltrimethoxysilane. It can be done easily can be prepared by a mixture of 200 g of 1-trimethoxysilyl-3-glycidoxypropane and stir 100 g water at room temperature until homogeneous. This solution is then added with 500 g Ethyl ether extracted. The aqueous phase is discarded. The ether solution contains 15.5 g of hydrolyzed silane.

The following examples, which describe representative embodiments of the invention, serve to further illustrate the invention. It should be noted that the examples are for illustrative purposes only and that with them It is only intended to enable those skilled in the art in question to use the invention in all of its forms to facilitate. The examples are therefore not intended to limit the invention or the claims.

example 1

30 parts by weight of bisphenol A bis (3-methacrylato-2-hydroxypropyl) ether are mixed with 70 parts by weight of triethylene glycol dimethacrylate. 100 parts by weight of this resin mixture are added to 100 parts by weight Calcium silicate fibers are added which have an average length of 5.5 microns, with 97 wt .- ^ of which a length of less than 20% and 94% by weight thereof a length of less than 10% have, and have diameters of 1/13 to 1/15 of the length. The fibers remain distributed in the resin mixture during long storage times

To 100 parts by weight of the resin / Paser mixture are 1.5 parts by weight N-bis- (2-hydroxyethyl) -p-toluidine, 0.6 part of benzoyl peroxide, and 0.05 part of 3-tert-butyl-4-methylphenol were added. The mass binds in approximately 100 seconds at room temperature

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and hardens in about 4 minutes from mixing. The physical properties of the hardened mass are:

2
Compressive strength, kg / cm 1260

2 Diametric tensile strength, kg / cm 266

Hardness, Rockwell H 91-94

Solubility in H ₃ O, g / cm (24 st) 1.42 χ Ι θ " ⁵

Water sorption, £ (24 st) 2.3

Volume shrinkage, % 3 »8

A human tooth is treated with a 5C TÜgen of phosphoric acid for 2 minutes etched, rinsed and dried. The above compound is applied to the tooth and allowed to harden. The tooth will then immersed in water at 37 C for 24 hours. The bond strength the mass on the adamantine of the tooth is then found to be 49 kg / cm, as an examination of the cut tooth shows also the tongue-shaped protrusions of the resin compound, which are in the Penetrate adamantine.

Example 2

A patient's teeth showing areas of eroded dentin and adamantine are etched for 2 minutes Treated phosphoric acid, washed, dried and then hydrolyzed with a 5 5 * solution of em gamma-methacryloxypropyltrimethoxysilane treated.

100 parts of the suspension of calcium silicate fibers in the resin mixture of Example 1 are divided into two equal portions of 50 parts each. 0.025 part of 3-tert-butyl-4-methylphenol are added to each serving. 0.6 parts of benzoyl peroxide are added to one portion and 1.5 parts of N-bis- (2-hydroxyethyl) -p-toluidine become to the other portion to ^ e-

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give · Equal parts of each serving are then mixed together and applied to the prepared teeth. The applied register is allowed to cure for approximately 20 minutes and then worked off and polished. A test after 6 months shows a 100% retention and a standstill of the erosion as well as an elimination of hypersensitivity.

Example 5

100 parts by weight of calcium silicate fibers as used in Example 1 were used with 0.6 parts by weight of benzoyl peroxide mixed·

To 100 parts by weight of the resin mixture of Example 1 are 0.05 part by weight of 3-tert-butyl-4-methylphenol and 1.5 parts by weight of N-bis (2-hydroxyethyl) p-toluidine were added.

The occlusal surfaces of molars that are developing Have damage, are etched with a 50 # phosphoric acid for 2 minutes, rinsed and dried.

The mixture of calcium silicate fibers and eenzoyl peroxide is mixed with the resin mixture and other ingredients and applied to the. applied to prepared teeth. The applied mixture penetrates the damage to the teeth and fills them up, which is based on a cut tooth with an electron microscope can be shown.

Example 4

A two-component system is prepared as in Example 2, except that the component with the catalyst 5 wt .- ^ Contains benzoyl peroxide and the component with the accelerator contains 1 wt .-? · N-Bi8- (2-hydroxyethyl) -p-toluidine.

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The teeth to be treated are first etched as in Example 2. Then the component with the ^ enzoyl peroxide applied to the tooth surface and spread out, in front then the component containing the accelerator is applied. The two layers interact with one another and polymerize for a period of 2 minutes after which time any unreacted material is wiped off. It becomes an excellent penetration and replenishment in the existing one developing damage is achieved by examining a cut tooth with an electron microscope can be determined.

Example 5

A patient's teeth that are due to a gingival erosion Have discolored areas are treated as in Example 2, except that 5 wt .- # titanium dioxide is added to the mass will. The presence of the titanium dioxide masks the discoloration and generally improves the appearance of the treated area.

Example 6

Example 1 is repeated, but using a mass in which the fiber filler makes up 30 wt .- ^ of the mass.

Example 7

Example 1 is repeated, but using a cash register in which the fiber filler makes up 70% by weight of the mass.

Example 8

60 parts by weight of bisphenol-A-bis-CS-retliacrylato ^ -hydroyvr rrpyl) - ether and 40 parts by weight of triethyleii ^ lycoldimethacrylate are mixed together, and the raised "jomisch becomes in two

3 0 9 ^ ? !? '1 H 7 Π

equal portions divided

The first portion is mixed with 0.06 i » butylated hydroxy toluene, 55 i * calcium silicate fibers as described in Example 1, 3 i» 3-tert-butyl-4-methylphenol and 0.70% benzoyl peroxide, whereby all percentages relate to the weight of the total mixture of the portion.

The second portion is mixed with 55 ^ calcium silicate fibers as described above, 0.06 # butylated hydroxytoluene, 3 % 3-tert-butyl-4-methylphenol and 3 ^ N-bis (2-hydroxyethyl) ptoluidine, where all percentages relate to the weight of the total mixture of the portion

A patient's teeth that show areas of eroded dentin and adamantine are soaked in 50% phosphoric acid for 2 minutes treated, rinsed with water and dried. The areas to be restored are then covered with a 5% solution of hydrolyzed gamma-methacryloxypropyltrimethoxysilane treated and dried

The two pieces of fiber filler and resin are then mixed together and the mixture is applied to the prepared teeth. The mass is allowed to harden for 20 minutes and then trimmed and polished with a diamond grinding wheel. A check after 6 months shows a 100 # retirement and a standstill of the erosion, as well as a disappearance of the hypersensitivity caused by the erosion.

Example 9

Example 8 is repeated, but the teeth are after Etching and drying with a 10% solution of gamina-glycidoxypropyltrimethoxysilane in acetone instead of gamma

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Methacryloxypropyltrimethoxysilane treated · There are increased Maintain bond strengths.

As mentioned above, the adhesive composition according to the invention is particularly suitable for the treatment of gingival eroded ones Surfaces, The complicated surgical procedures previously required to treat gingival erosion, are no longer necessary. The preparation for the application of the mass according to the invention only requires that the to be treated Tooth is etched with a cleaning agent and carefully dried. A primer with an anchoring agent is preferred, but not necessary.

The success in the treatment of gingival erosion with the adhesive restorative cash register according to the invention results emerged from a study in which 207 teeth were treated in the mouth of patients and then followed for 6 months. At this Study consisted of the only preparation of the treated teeth in an etching with a 5 ^ ^ phosphoric acid during approximately 2 minutes followed by thorough drying of the teeth. The adhesive material remained in 202 cases stick firmly. The mass went short in 5 of the treated teeth declined after application, but reapplied following removal of precarious adaitantin resulted a firm bond. In each case the following procedure was used.

The material used was that of the example above. For prophylaxis only pumice stone was used, after which the gingival erosion was treated for 2 minutes for the purpose of etching with a 50% phosphoric acid and the etchant spreading over the entire adjacent areas of the adamantine

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extended. The contact of the gingival tissue with the etchant did not produce any adverse reactions · Following the etching, the surface was rinsed with water before rinsing washed 'and the surfaces were isolated and carefully dried with warm air. The one used for drying Air should be free of oil. As in Example 8 above, the adhesive box carefully mixed and applied to the tooth with a polypropylene or tetrafluoroethylene spatula and up processed to the desired thickness and shape. The material leaked on the adjacent non-eroded adamantine relaxed and resulted in an excellent feather edge. The finished work was carried out after about 20 minutes to avoid breaking the initially weak bonds. After this time, the protruding material was removed with a diamond or a granulite and polished. With a probe no edges were found

When the treated teeth were examined after 6 months, there was no erosion behind the edges of the mass, nor any The formation of cavities or edge erosion can be detected. There were no contraindications to the use of the adhesive mass can be determined.

In the five cases in which the originally applied mass came off again, it was suspected that this was the reason for this in the presence of precarious brownish dentin or possible moisture contamination prior to the initial Setting lay.

Vie already mentioned makes the invention adhesive Conservative treatment of gingival erosion is possible, thereby eliminating a hypersensitivity and the appearance

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is greatly improved. The material has excellent flow properties, which is ideal for the preparation of a gingival erosion is very important. It can be drained and easily condensed substantially without the use of pressure. The finished margins are characteristically not detectable with a probe, because the material is in the tooth structure flows with a degree of adaptation that is normally found with dental filling materials. The present The invention thus allows the treatment of gingival erosion without any surgical procedure or without any damage to healthy tooth parts to achieve retention. The adhesive restorative material can be used without an operative technique, the pretreatment only consists of acid etching to restore demineralized tooth structures, to cover discoloration, broken ones To restore edges without becoming matt, to repair and coat old amalgam fillings, edges of To seal previous fillings, to improve hypersensitivity following a tooth fracture, various hypersensitive ones Cover areas, fill developing permanent teeth damage, and treat gingival erosions.

Claims;

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Claims (26)

PATENT CLAIMS; Fili adhesive restorative dental compound, characterized in that it consists of a suspension of filler fibers in a liquid polyacrylate resin composition in which the resin has a viscosity of less than 5000 centipoise and the fibers have a length of 1 to 100 µm and a diameter of 1/20 to 1/5 of the length, and consists of a peroxide catalyst and an accelerator for the resin. 2. Hasse according to claim 1, characterized in that the pasers make up 30 to 70 G-ew .- # of the mass. 3. Mass according to claim 2, characterized in that the fibers inorganic fibers with a hardness on the Mohs scale from 3 »5 to 6 are. 4. Composition according to claim 2, characterized in that the fibers consist of calcium silicate. 5 · Cash register according to claim 2, characterized in that the pasers have been treated with an anchoring agent. 6. Adhesive restorative dental material, characterized in that it consists of a suspension of filler fibers is a liquid polyacrylate resin composition, wherein the resin composition has a viscosity of less than 50C0 Centipoise and the pasers are 1 to 100u in length and 1/20 to 1/5 in diameter in length and wherein the resin composition is from about 25 to about 309828/1 070 % By weight of a compound (A) of the formula 0 0 CH ₂ = C - C 0 / & C - C = CH. R ₁ R ₁ wherein R _{1 is} hydrogen or alkyl having 1 to 4 carbon atoms;
R stands for the following: a) (CH ₂ CH-O) _x , where χ is an integer from 1 to R ₂ 5 represents and R _{2 represents} hydrogen or alkyl of 1 to 4 carbon atoms; b) CH ₂ (CH ₂ ) ^ CH ₂ O, where y is an integer of 1 or 2; OH OH I I c) -CH ₂ CH-CH ₂ OCH ₂ CH ₂ CH ₂ CH ₂ OCH ₂ Ch-CH ₂ O-; or d) -CH ₂ CH-CH ₂ O-, where R ^ is -OH or -0-CC = CH ₂ i 0 R ₁ ßehx and R _{1 have} the same meaning as above; and from 10 to 75% by weight of an aromatic or alicyclic polyacrylate compound (B). 7. Composition according to claim 6, characterized in that the filler makes up 30 to 70 percent by weight of the composition. 8. Composition according to claim 7, characterized in that R stands for (a), R ₁ stands for methyl and R ₂ stands for hydrogen. 309828/107 0 9. Composition according to claim 7, characterized in that B is a diaromatic diacrylate. 10. Composition according to claim 8, characterized in that B is a diaromatic diacrylate. 11. Mass according to claim 7, characterized in that B a bisphenol A bis (3-methacrylato-2-hydroxypropyl) ether is. 12. Composition according to claim 8, characterized in that B a bisphenol A bis (3-methacrylato-2-hydroxypropyl) ether is. 13. Composition according to claim 7, characterized in that A is triethylene glycol dimethacrylate. 14. Composition according to claim 12, characterized in that A is triethylene glycol dimethacrylate. 15. Composition according to claim 7, characterized in that the fibers are inorganic fibers with a hardness of 3.5 to 6 on the Kohs scale. 16. Composition according to claim 7 »characterized in that the fibers consist of calcium silicate. 17. Adhesive restorative dental material, characterized in that it consists of a suspension of 30 to 70 wt .- # calcium silicate fibers in a liquid resin composition, the fibers having a length of 1 to 100 μ and a diameter of 1/20 to 1/5 of length, where 309828/1070 the parsers are have an average length of 5.5 Ji, 97 wt .- # of the fibers have a length ρ of less than 20 and 94 wt -.% of the fibers have a length of Veniger than 10 ^ possess i, where also the resin composition wherein the composition consists of 30 to 70 wt .- # triethylene glycol dimethacrylate and 70 to 30 wt. ~% of bisphenol-a-bis- (3-methacrylato-2-hydroxypropyl) ether and a viscosity of not more than 5000 centipoise, and contains a peroxide catalyst and an amine accelerator. 18. Composition according to claim 17, characterized in that the fibers have been treated with a silane anchoring agent are. 19. Mass according to claim 17, characterized in that the fibers make up about 55 wt .- ^ of the mass that the Bath composition of about 40 wt .- # triethylene glycol, dimethacrylate and 60 wt .- ^ bisphenol-A-bis (3-methacrylato-2-hydroxypropyl) -ether and that the accelerator consists of N-bis- (2-hydroxyethyl) -p-toluidine and the catalyst Benzoyl peroxide consists. 20 · Procedure for repairing damage to the surface of a tooth, characterized.deösman on the Damage to an initially liquid, abbijadeiide, adhesive, applying dental restoration compound nachjüisetzt 1 and the Let the mass harden in situ on the Zafan. 21. Vepfairen according to claim 20, characterized in that jjaetfüer tooth first with a 50 to 85 # phosphoric acid is cleaned. 309828/1070 Dr. RICHARD KNEIÖSL PATENT ADVOCATE approached • MONKS · Mülteretraß · 31 Telephone SOeoeO 7th ^{MAR · Ιν // ύ} LEE PHARMACEUTICALS PATENT CLAIMS 20. Adhesive restorative dental material, consisting of two components to be mixed with one another before use, thereby marked that the components consist of the following: (a) a suspension of a liquid in Püllstoffasern PoIyacrylatharzzusanmensetzung, in which the resin has a viscosity of less than 5000 centipoise and the fibers μ a Länjre from 1 to 100 and have a diameter of from 1/20 to 1/5 of the length, and a*. Accelerator for the resin; (b) a suspension of filler fibers in a liquid polyacrylate resin composition, in which the resin has a viscosity less than 5000 centipoise and the fibers a length from 1 to 100 μ and a diameter of 1/20 to 1/5 of the length own, and a peroxide catalyst for the resin. 21. Cash register according to claim 20, characterized in that the amount of fibers is 30 to 70% by weight, based on each resin composition, matters. 22. Cash register according to claim 21, characterized in that the fibers are silicate fibers. 309828/1070 ^l * received on ...! 23 · Cash register according to claim 22, characterized in that the KarzzusairjT. Consists of about 25 to about 90 percent by weight of a compound A of the formula O O it I! CH- = C - C O / RT - C - C = CH- ² II ² R ₁ R ₁ wherein R _{1 is} hydrogen or alkyl having 1 to H carbon atoms;
R stands for the following: a) (CH-CH-O), where χ is an integer from 1 to 5 ^R 2 and R _{2 is} hydrogen or alkyl having 1 to ¹ ^ carbon atoms; b) CH ₂ (CH ₂ ) CH ₂ O, where y is an integer of 1 or 2; OH OH c) -CH ₂ CH-CH ₂ OCH ₂ CH ₂ CH ₂ Ch ₂ OCH ₂ CH-CH ₂ O-; or d) -CH-CH-CH-O-, where R- is -OK or -0-C-C = CH R. -CH-CH-O-, where R- for -OK cder -0-CC = CH _n ² I ² 3 Ii I 2 0 R ₁ and R _{1 has} the same meaning as above; and consist of 10 to 75 parts by weight of an aromatic or alicyclic polyacrylate compound (B). 24. Cash register according to claim 23, characterized in that R stands for (a); R _{1 represents} methyl and R- represents hydrogen. 25 · Cash register according to claim 23, characterized in that · · Ξ consists of bisphenol-A-bis (3-methacrylato-2-hydroxyproryl) ether 26. Composition according to claim 25, characterized in that £ A from Triethyleneglyko'ldimethacrylat consists. 309828/1070 * "^ 'BAD ORIGINAL