DE102023123022A1 - Composition for use as a dental adhesive or for use as a component of a multi-component dental adhesive and manufacturing process and applications - Google Patents

Abstract

A composition is described which is suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive. Methods for producing a composition according to the invention are also described. A composition according to the invention for use in a method for surgical or therapeutic treatment of the human or animal body and/or for use in a diagnostic method which is carried out in the human or animal body is also described. A method for the therapeutic treatment of teeth is also described.

Description

The present invention relates to a composition suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive. The present invention further relates to methods for producing a composition according to the invention. The invention also relates to a composition according to the invention for use in a method for surgical or therapeutic treatment of the human or animal body and/or for use in a diagnostic method carried out in the human or animal body. The invention also relates to a method for the therapeutic treatment of teeth.

The invention is defined in the appended claims. Preferred aspects of the present invention will also become apparent from the following description, including the examples.

Insofar as certain embodiments are designated as preferred for an aspect of the invention, the corresponding statements also apply to the other aspects of the present invention, mutatis mutandis. For example, the statements on preferred embodiments of a composition according to the invention also apply to production processes according to the invention, and vice versa, mutatis mutandis. Preferred individual features of aspects of the invention (as defined in the claims and/or disclosed in the description) can be combined with one another and are preferably combined with one another, unless the person skilled in the art concludes otherwise from the present text in the individual case.

• (1) „ Systematic review of the chemical composition of contemporary dental adhesives“ von Van Landuyt et al. in Biomaterials 28(2007) 3757-3785 ;
• (2) „ Looking for the ideal adhesive - A review“ von Sezinando in Revista Portuguesa de Estomatologia, Medicina Dentaria e Cirurgia Maxilofacial, 2014, 55(4): 194-206 ;
• (3) „ Classification review of dental adhesive systems: from the IV generation to the universal type“ von Sofan et al. in Annali di stomatologia, 2017, VIII(1):1-17 ;
• (4) „ 10-MDP Based Dental Adhesives: Adhesive Interface Characterization and Adhesive Stability - A Systematic Review“ von Carrilho et al. in Materials, 2019, 12, 790 .

Compositions for use as dental adhesives are already known from the state of the art and are described, for example, in the following publications:

• (1) " Systematic review of the chemical composition of contemporary dental adhesives” by Van Landuyt et al. in Biomaterials 28(2007) 3757-3785 ;
• (2) " Looking for the ideal adhesive - A review” by Sezinando in Revista Portuguesa de Estomatologia, Medicina Dentaria e Cirurgia Maxilofacial, 2014, 55(4): 194-206 ;
• (3) " Classification review of dental adhesive systems: from the IV generation to the universal type” by Sofan et al. in Annali di stomatologia, 2017, VIII(1):1-17 ;
• (4) " 10-MDP Based Dental Adhesives: Adhesive Interface Characterization and Adhesive Stability - A Systematic Review” by Carrilho et al. in Materials, 2019, 12, 790 .

Compositions for use as dental adhesives are used in dentistry and are used there in particular for attaching filling material or dentures to the tooth (dentin). Since the restoration of teeth usually aims to achieve a permanent and firm hold between the tooth and the filling material or denture used, which must above all withstand the mechanical stresses that occur regularly (for example through chewing), the aim in practice is to use compositions for use as dental adhesives or dental adhesive compositions that have the highest possible shear bond strength.

Against this background, the primary object of the present invention was to provide a composition for use as a dental adhesive or for use as a component of a dental multi-component adhesive, which has a high shear bond strength (preferably > 25 MPa in a shear bond strength test with a recessed blade according to ISO 29022:2013 - Dentistry - Adhesion - Shear bond strength test with a recessed blade), in particular for the field of application of bonding dentin (biological tooth material) to dental restorations and dental composites (synthetic tooth fillings, etc.) under light curing. Furthermore, the composition to be provided should preferably enable the achievement of a high quality for the hybrid layer that forms after the composition has been applied to the tooth (for the term hybrid layer, see the above-mentioned publication (4), Carrilho et al., page 12, last full paragraph). In addition, the composition to be provided should preferably contribute to reducing the risk of dentin avulsion, since cohesive dentin failure is to be avoided from a clinical point of view.

The composition to be specified should, in addition to excellent shear bond strength, preferably also have excellent storage stability.

A related further object of the present invention was to provide methods for producing corresponding compositions (according to the invention) for use as a dental adhesive or for use as a component of a dental multi-component adhesive.

Furthermore, the invention should take into account that the composition to be provided is suitable for use in a method for surgical or therapeutic treatment of the human or animal body and/or for use in a diagnostic method that is carried out on the human or animal body, in particular is suitable for use in a therapeutic method in the field of dentin-adhesive fixation.

Further tasks and associated technical effects emerge from the following description and the patent claims.

1. a) ein oder mehreren Filmbildnern ausgewählt aus der Gruppe bestehend aus Polymeren, deren Wiederholungseinheiten strukturelle Einheiten gemäß Formel (I) sind oder umfassen
   
   wobei für R¹, R², R³, R⁴ und R⁵ in jeder strukturellen Einheit unabhängig voneinander gilt:
   • R¹ bedeutet eine Alkoxygruppe mit insgesamt 1 bis 10 Kohlenstoffatomen oder eine Phenylgruppe,
   • R² und R³ sind gleich oder verschieden und jeweils ausgewählt aus der Gruppe bestehend aus H und Strukturen der Formel (II)
     
     mit
     • X ist H oder CH₃
     • und
     • L ist ausgewählt aus der Gruppe bestehend aus Alkylengruppen mit insgesamt 2 bis 10 Kohlenstoffatomen,
     • oder bildet zusammen mit einem benachbarten Sauerstoffatom eine Polyethylenglycolgruppe oder eine Polypropylenglycolgruppe,
       • wobei vorzugsweise die Polyethylenglycolgruppe und/oder die Polypropylenglycolgruppe eine Kettenlänge n (d.h. eine Anzahl an Wiederholeinheiten) im Bereich von 1 bis 10 aufweist,
     • und
     • R⁴ und R⁵ sind gleich oder verschieden und jeweils
       • eine Einfachbindung
       • oder
       • eine Alkylengruppe mit insgesamt 1 bis 4 Kohlenstoffatomen, wobei vorzugsweise R⁴ und R⁵ in Summe nicht mehr als 4 Kohlenstoffatome aufweisen,
   • wobei die Zusammensetzung geeignet ist zur Verwendung als dentales Adhäsiv oder zur Verwendung als Komponente eines dentalen Mehrkomponentenadhäsivs.

The primary object of the present invention is achieved by a composition comprising or consisting of

1. a) one or more film formers selected from the group consisting of polymers whose repeating units are or comprise structural units according to formula (I)
   
   where R ¹ , R ² , R ³ , R ⁴ and R ⁵ in each structural unit independently of one another:
   • R ¹ represents an alkoxy group having a total of 1 to 10 carbon atoms or a phenyl group,
   • R ² and R ³ are the same or different and are each selected from the group consisting of H and structures of the formula (II)
     
     with
     • X is H or CH ₃
     • and
     • L is selected from the group consisting of alkylene groups with a total of 2 to 10 carbon atoms,
     • or forms together with an adjacent oxygen atom a polyethylene glycol group or a polypropylene glycol group,
       • wherein preferably the polyethylene glycol group and/or the polypropylene glycol group has a chain length n (ie a number of repeat units) in the range from 1 to 10,
     • and
     • R ⁴ and R ⁵ are the same or different and each
       • a single bond
       • or
       • an alkylene group having a total of 1 to 4 carbon atoms, wherein R ⁴ and R ⁵ preferably have a total of not more than 4 carbon atoms,
   • wherein the composition is suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive.

Preferably, R ¹ is a methoxy group (alkoxy group with 1 carbon atom) or phenyl group, preferably a methoxy group.

Preferably, R ⁴ and R ⁵ are each a single bond.

Preferably L is an alkylene group having 2 or 3 carbon atoms, preferably 2 carbon atoms.

• R¹ ist eine Methoxygruppe (Alkoxygruppe mit 1 Kohlenstoffatom), R⁴ und R⁵ sind jeweils eine Einfachbindung, L ist eine Alkylengruppe mit 2 oder 3 Kohlenstoffatomen, vorzugsweise mit 2 Kohlenstoffatomen.

At the same time, the following is particularly preferred:

• R ¹ is a methoxy group (alkoxy group with 1 carbon atom), R ⁴ and R ⁵ are each a single bond, L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

A composition consisting of a) a film former (as defined above) is the film former polymer itself, with its molecular weight distribution resulting from the synthesis and with the variations in the arrangement of repeating units resulting from the synthesis.

A composition consisting of a) several film formers is a mixture of two or more such film former polymers.

Surprisingly, it has been found that the use of one or more of the above-defined film formers in compositions according to the invention for use as a dental adhesive or for use as a component of a dental multi-component adhesive has a particularly positive influence on the shear bond strength of the corresponding composition.

• Anfließverhalten: dieses wird durch den Filmbildner beeinflusst und beschreibt die Wechselwirkung zwischen Oberfläche und Adhäsiv durch attraktive bzw. repulsive Kräfte. Häufigste Messung dieser Größe: Kontaktwinkel. Vorteilhaft ist in der Regel ein sehr geringer Kontaktwinkel zum Substrat; ein aufgebrachtes Adhäsiv hat dann bereits durch physikalische Phänomene einen starken Kontakt zur Oberfläche.

The use of film formers in compositions for use as a dental adhesive or for use as a component of a dental multi-component adhesive primarily results in an increase in the surface quality of a layer of the corresponding composition applied, for example, to the tooth to be treated (the dentin). The use of one or more of the film formers defined above results in an excellent surface quality, which is often perceived as improved in direct comparison with film formers known from the prior art. The person skilled in the art often evaluates the surface quality by taking into account or determining one or more of the following properties:

• Flow behavior: this is influenced by the film former and describes the interaction between surface and adhesive through attractive or repulsive forces. Most common measurement of this value: contact angle. A very small contact angle to the substrate is generally advantageous; an applied adhesive then already has strong contact with the surface through physical phenomena.

Homogeneity of the resulting surface: The adhesive film is obtained by evaporating the volatile components (e.g. solvents) of typical compositions for use as dental adhesives. This involves the application of force and thus movement of the liquid composition. Since the viscosity generally increases during evaporation, the surface of the film that is being formed is not always perfectly leveled. Films or layers of poor quality are topographically characterized by "hills and valleys", craters and the like. Such inhomogeneities introduce potential defect sites into the dental restoration as early as the step of applying and drying the composition. The use of one or more of the above-defined film formers in compositions according to the invention for use as a dental adhesive or for use as a component of a dental multi-component adhesive results in uniform films or layers with only a slight degree of disturbing topographical structures (as described above) when the volatile components evaporate, compared with the prior art.

Initial stickiness/grip: In a classic composite structure, a small amount of material is transferred to the applied adhesive film using dental tools. It is desirable that the composite detaches readily from the tool. To achieve this, the physical shear bond strength between the adhesive composition and the composite (initial stickiness/grip) must be greater than that between the composite and the tool. The use of one or more of the film formers defined above in compositions according to the invention for use as a dental adhesive or for use as a component of a dental multi-component adhesive is advantageous in this respect.

It was surprising to observe that the use of one or more of the above-defined film formers in compositions for use as dental adhesives not only has a positive influence on the surface quality of the layers made from the corresponding compositions, but also causes a significant increase in the shear bond strength of corresponding compositions according to the invention.

Preferably, the number of structural units according to formula (I) in the macromolecules of the (film-forming) polymer is in the range from 500 to 2000, particularly preferably in the range from 600 to 1600, very particularly preferably in the range from 700 to 1400.

Also preferably, the molecular weight (MW) of the macromolecules of the (film-forming) polymer is in the range of 100,000 Da to 450,000 Da, particularly preferably in the range of 200,000 Da to 400,000 Da.

) wird zum Ausdruck gebracht, dass die mit dem Buchstaben „L“ bezeichnete Einheit über eine kovalente Bindung mit der strukturellen Einheit gemäß Formel (I) verbunden ist, das heißt im Falle des Vorliegens der Struktur gemäß Formel (II) diese über eine kovalente Bindung mit dem Sauerstoffatom verbunden ist, welches in der allgemeinen Formel (I) eine Bindung zu der Einheit „R^z“ ausbildet und/oder über eine kovalente Bindung mit dem Sauerstoffatom verbunden ist, welches in der allgemeinen Formel (I) eine Bindung zu dem Element „R³“ ausbildet. The “snake line” contained in formula (II) (

) it is expressed that the unit designated by the letter "L" is linked via a covalent bond to the structural unit according to formula (I), that is to say, in the case of the presence of the structure according to formula (II), this is linked via a covalent bond to the oxygen atom which in the general formula (I) forms a bond to the unit "R ^z " and/or is linked via a covalent bond to the oxygen atom which in the general formula (I) forms a bond to the element "R ³ ".

• b) als Haftvermittler ein oder mehrere polymerisierbare Monomere, wobei das eine oder die mehreren polymerisierbaren Monomere des Bestandteils b) ein oder mehrere acide funktionelle Gruppen aufweisen, und/oder
• c) ein oder mehrere weitere polymerisierbare Monomere, wobei das eine oder die mehreren weiteren polymerisierbaren Monomere des Bestandteils c)
  • von dem einen oder den mehreren polymerisierbaren Monomeren des Bestandteils b) verschieden sind, und
  • ausgewählt sind aus der Gruppe bestehend aus Acrylaten, Methacrylaten, Acrylamiden und Methacrylamiden,
  und/oder
• d) ein oder mehrere Photoinitiatoren, und/oder
• e) ein oder mehrere Inhibitoren (auch als Stabilisatoren bezeichnet), und/oder
• f) als Füllstoff nicht-aggregierte und nicht-agglomerierte Füllstoffpartikel mit einer Partikelgröße im Bereich von 7 bis 70 nm, wobei die Füllstoffpartikel Siliciumdioxid(SiO₂)-Partikel und/oder Ytterbiumtrifluorid(YbF₃)-Partikel sind, und/oder
• g) ein oder mehrere Lösungsmittel, bevorzugt ein oder mehrere Lösungsmittel ausgewählt aus der Gruppe bestehend aus Wasser, Ethanol, Isopropanol und Aceton, und/oder
• h) ein oder mehrere Co-Initiatoren, bevorzugt ausgewählt aus der Gruppe bestehend aus Aminen und Boranen, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus tertiären Aminen,

Preferably, a composition according to the invention additionally comprises as one or more further components:

• b) as adhesion promoter one or more polymerizable monomers, wherein the one or more polymerizable monomers of component b) have one or more acidic functional groups, and/or
• c) one or more further polymerizable monomers, wherein the one or more further polymerizable monomers of component c)
  • are different from the one or more polymerizable monomers of component b), and
  • are selected from the group consisting of acrylates, methacrylates, acrylamides and methacrylamides,
  and/or
• d) one or more photoinitiators, and/or
• e) one or more inhibitors (also called stabilizers), and/or
• f) as filler, non-aggregated and non-agglomerated filler particles having a particle size in the range of 7 to 70 nm, wherein the filler particles are silicon dioxide (SiO ₂ ) particles and/or ytterbium trifluoride (YbF ₃ ) particles, and/or
• g) one or more solvents, preferably one or more solvents selected from the group consisting of water, ethanol, isopropanol and acetone, and/or
• h) one or more co-initiators, preferably selected from the group consisting of amines and boranes, particularly preferably selected from the group consisting of tertiary amines,

The one or more acidic functional groups of the one or more polymerizable monomers of component b) contribute to a preferably acidic pH value in corresponding compositions. A composition according to the invention with a pH value in the range from 1 to 4.5 is preferred.

The one or more other polymerizable monomers of component c) form the polymer matrix in appropriate compositions together with the monomers of component b). Properties such as hydrophilicity, adhesion and cohesion strength, degree of linkage of the resulting polymer network, flexibility, etc. are all controlled by the choice of polymer matrix.

The one or more photoinitiators of component d) enable, in appropriate compositions, light-curing and the processing speeds usual in modern dentistry; due to the presence of photoinitiators, polymerization can be carried out in a short time.

The one or more inhibitors (also known as stabilizers) of component e) help to achieve sufficient storage stability in appropriate compositions. Due to their high affinity for radicals, they form stable reaction products with them and thus prevent premature (often thermal) polymerization processes.

The use of non-aggregated and non-agglomerated filler particles according to component f) advantageously reduces the number of tears or the risk of tears occurring. Furthermore, the use of non-aggregated and non-agglomerated filler particles according to component f) has a structure-reinforcing effect, so that the use of non-aggregated and non-agglomerated filler particles according to component f) can, for example, result in a (further) shift in the cohesive fracture limit to higher values. The use of ytterbium trifluoride particles also advantageously leads to an increase in radiopacity, so that when ytterbium trifluoride particles are used, a dentin-like radiopacity can preferably be achieved.

The particle size distribution of the non-aggregated and non-agglomerated filler particles of component f) is preferably determined by means of dynamic light scattering, for example on a ZetaSizer Nano ZS from Malvern. For this purpose, the filler particles to be examined are finely dispersed in a suitable solvent using ultrasound and then measured at a wavelength of, for example, 633 nm. The data obtained on the volume-weighted particle size distribution are evaluated and displayed, for example using the ZetaSizer software V7.13. A particle size in the sense of the present invention is then understood to mean the d50 values obtained in this way in a volume-weighted evaluation.

Preferably, a preferred composition according to the invention comprises silicon dioxide particles and also ytterbium trifluoride particles (i.e. both types of particles) as non-aggregated and non-agglomerated filler particles according to component f).

In many cases, the solvents in component g) are used in particular to make the other ingredients compatible, to homogenize and to influence the flow behavior. When acting on the tooth, they can stabilize the exposed collagen fibers during resin infiltration. The higher vapor pressure of the organic solvents makes it easier to remove water in the evaporation step. They often act as entrainers and/or azeotrope formers.

In the case of multi-component systems, the co-initiators according to component h) can be included in one, several or all components. Co-initiators act as radical carriers. For example, the initiator camphorquinone cannot transfer its excited state satisfactorily to the unsaturated substrates on its own. Co-initiators can be viewed as mediators that form reactive radicals by abstracting hydrogen from the excited camphorquinone, which are then easily transferred to the substrates. A classic example of the interplay between initiator and co-initiator is the camphorquinone/amine synergism, which is adequately described in the relevant literature.

Further preferred is a composition according to the invention, wherein the one or more further polymerizable monomers of component c) are each either monofunctional or oligofunctional,
and/or
amphiphilic or hydrophobic.

The selection of functionality is crucial for setting the physical properties of the cured product. Pure monofunctionality leads exclusively to linear chain growth. Oligofunctional monomers are suitable for cross-linking and thus have a significant influence on relevant physical properties such as tensile strength, flexibility and brittleness.

The degree of hydrophilicity influences (i) the interaction with the tooth structure and the subsequently applied (usually hydrophobic) dental composite and (ii) the extent of potential water retention, which influences the swelling of the polymer network and thus also the dimensional stability.

• für Siliciumdioxid-Partikel im Bereich von 10 bis 15 nm liegt und/oder
• für Ytterbiumtrifluorid-Partikel im Bereich von 7 bis 60 nm liegt, bevorzugt im Bereich von 7 bis 50 nm, besonders bevorzugt im Bereich von 20 bis 40 nm.

Also preferred is a composition according to the invention, wherein
the filler particles of component f) are surface-modified,
and/or
the particle size of the filler particles of component f)

• for silicon dioxide particles in the range of 10 to 15 nm and/or
• for ytterbium trifluoride particles is in the range of 7 to 60 nm, preferably in the range of 7 to 50 nm, particularly preferably in the range of 20 to 40 nm.

In comparative screenings of compositions according to the invention in which the aforementioned non-aggregated and non-agglomerated filler particles with the aforementioned preferred particle sizes were used, a particularly high shear bond strength was obtained.

The ytterbium trifluoride particles are preferably surface-modified with methacryloylphosphoric acid or a derivative thereof, particularly preferably with MDP. MDP refers to 10-[(2-methylprop-2-enoyl)oxy]decyl dihydrogen phosphate (CAS No. 85590-00-7). The silicon dioxide particles are preferably surface-modified with methacrylsilane or a derivative thereof, particularly preferably with MPS. MPS refers to [3-(methacryloyloxy)propyl]trimethoxysilane (CAS No. 2530-85-0).

A composition according to the invention is preferred, wherein
the ratio of the total mass of component c) to the total mass of the one or more film formers a) is in the range from 4.5:1 to 96:1, preferably in the range from 10:1 to 15:1,
and/or
the ratio of the total mass of component c) to the total mass of component f) is in the range from 2.25:1 to 96:1, preferably in the range from 3:1 to 6:1,
and/or
the ratio of the total mass of the one or more film formers a) to the total mass of component f) is in the range from 1:20 to 10:1, preferably in the range from 1:3 to 1:1.

Compositions according to the invention, in which one or more, preferably all of the above-mentioned ratios are established, convince in comparative tests by the high shear bond strength achieved.

Also preferred is a composition according to the invention, preferably a preferred composition according to the invention comprising the one or more film formers a) in an amount of up to 10 percent by weight, preferably in an amount in the range from 1 to 10 percent by weight, particularly preferably in an amount in the range from 2 to 8 percent by weight,
and/or
component b) in an amount ranging from 1 to 5 percent by weight,
and/or
component c) in an amount ranging from 45 to 79 percent by weight,
and/or
the component d) in an amount in the range of 0.1 to 3.5 percent by weight, preferably in the range of 0.1 up to 1.5 percent by weight,
and/or
the component e) in an amount ranging from 0.01 to 0.5 percent by weight,
and/or
component f) in an amount ranging from 1 to 20 percent by weight,
and/or
the component g) in an amount in the range of 7.5 to 35 percent by weight, preferably in the range of 10 to 27.5 percent by weight, particularly preferably in the range of 15 to 25 percent by weight, very particularly preferably in the range of 17.5 to 20 percent by weight,
and/or
the component h) in an amount ranging from 0.1 to 2 percent by weight,
each based on the total mass of the composition.

The adjustment of the aforementioned preferred ratios and/or proportions advantageously leads to compositions according to the invention with a particularly high shear bond strength.

• wobei der eine oder die mehreren Initiatoren des Bestandteils i) von den ein oder mehreren Photoinitiatoren des Bestandteils d) verschieden sind,
• und wobei die Bestandteile b) und c), bevorzugt die Bestandteile b), c) und die ein oder mehreren Filmbildner a), getrennt von dem Bestandteil i), bevorzugt getrennt von den Bestandteilen g) und i), vorliegen.

A composition according to the invention is preferred, wherein the composition is multicomponent,
wherein the composition preferably comprises as a further component i) initiators for chemical curing, particularly preferably for chemical curing at ambient temperature,

• wherein the one or more initiators of component i) are different from the one or more photoinitiators of component d),
• and wherein components b) and c), preferably components b), c) and the one or more film formers a), are present separately from component i), preferably separately from components g) and i).

The one or more co-initiators according to component h) differ from the initiators of component i) in that the one or more co-initiators according to component h) cannot function as initiators for chemical curing within the meaning of the present invention.

For the above-mentioned components or groups of components of the multi-component composition within the meaning of the present invention, “separate” means that they are contained in different, spatially separated components of the multi-component composition.

The preferred spatial separation of components b) and c), preferably components b), c) and the one or more film formers a) from component g), ensures that any components susceptible to hydrolysis or solvolysis are separated from the solvent. This increases storage stability.

• - einer ersten Komponente umfassend die ein oder mehreren Filmbildner a) und die Bestandteile b), c), d), e) und f), und
• - einer zweiten Komponente umfassend die Bestandteile g) und i),

wobei die erste und die zweite Komponente jeweils als separate Einzelkomponenten (d.h. räumlich getrennt voneinander) vorliegen.Further preferred is a multi-component composition according to the invention, wherein the composition is two-component, consisting of

• - a first component comprising the one or more film formers a) and the components b), c), d), e) and f), and
• - a second component comprising components g) and i),

wherein the first and second components are each present as separate individual components (i.e. spatially separated from one another).

The advantages of spatial separation outlined above apply accordingly. Preferably, measures are taken to design the second component in such a way that it is stable in itself and can be easily mixed with the first component. In this respect, the second component is preferably designed in such a way that the solvent(s) of component g) is/are inert towards the one or more initiators of component i).

• wobei der Bestandteil j) in der zweiten Komponente vorzugsweise in einer Menge im Bereich von 0,1 bis 2 Gewichtsprozent enthalten ist, bezogen auf die Gesamtmasse der zweiten Komponente.

Also preferred is a multicomponent composition according to the invention, wherein
the component g) is contained in the second component in an amount in the range of 50 to 99 percent by weight, preferably in the range of 80 to 98 percent by weight, based on the total mass of the second Component,
and/or
the one or more initiators of component i) are selected from the group consisting of peroxides, redox initiators and initiators for chemical, non-radiative curing, preferably selected from the group consisting of sulfinates and borates and particularly preferably selected from the group consisting of sodium toluene sulfinate and four-coordinated borates,
and/or
the component i) is contained in the second component in an amount in the range of 0.1 to 10 percent by weight, preferably in the range of 1 to 5 percent by weight, based on the total mass of the second component,
and/or
the second component comprises as an additional component j) one or more solubilizers, preferably 2-butanone,

• wherein component j) is preferably contained in the second component in an amount in the range of 0.1 to 2 percent by weight, based on the total mass of the second component.

In the context of the present invention, the term "nonradiative" means that the corresponding initiators are suitable for carrying out curing without the external influence of radiation. Irradiation with light is therefore not absolutely necessary when using initiators for chemical, nonradiative curing.

Also preferred is a multi-component composition according to the invention, wherein the first component
which comprises one or more film formers a) in an amount ranging from 1 to 10 percent by weight,
and/or
component b) in an amount ranging from 1 to 5 percent by weight,
and/or
component c) in an amount ranging from 45 to 96 percent by weight,
and/or
component d) in an amount ranging from 0.1 to 1.5 percent by weight,
and/or
component (e) in an amount ranging from 0.01 to 0.5 percent by weight,
and/or
component f) in an amount ranging from 1 to 20 percent by weight,
each based on the total mass of the first component.

The setting of the aforementioned preferred proportions in the first component of a preferably inventive multi-component composition advantageously leads to preferably inventive multi-component compositions with which a particularly high shear bond strength can be achieved.

Preferably, a composition according to the invention, preferably a preferred composition according to the invention, as defined above or below, comprises
the one or more film formers a) in an amount in the range of 5 to 8 percent by weight, preferably in the range of 6 to 8 percent by weight,
and/or
the component f) in an amount in the range of 2 to 15 percent by weight, preferably in the range of 5 to 12 percent by weight, particularly preferably in the range of 6 to 8 percent by weight,
each based on the total mass of the composition.
Also preferred is a composition according to the invention, wherein
the filler particles of component f) are silicon dioxide particles and component f) is contained in the composition in an amount in the range of 2 to 8 percent by weight, preferably in the range of 5 to 6 percent by weight, based on the total mass of the composition,
or
the filler particles of component f) are ytterbium trifluoride particles and component f) is contained in the composition in an amount in the range of 12 to 15 percent by weight, based on the total mass of the composition, or
component f) consists of 2 to 4 percent by weight of silicon dioxide particles and 2 to 4 percent by weight of ytterbium trifluoride particles, preferably 3 percent by weight of silicon dioxide particles and 3 weight percent of ytterbium trifluoride particles, each based on the total mass of the composition.

It has been shown that the setting of the aforementioned preferred amounts of film former a) and/or filler particles f) in compositions according to the invention has a particularly advantageous effect on the level of the achievable shear bond strength. In particular, it was observed that the shear bond strength can be significantly increased again when both silicon dioxide particles and ytterbium trifluoride particles are used as filler particles f), which can probably be attributed to the occurrence of a synergistic effect when silicon dioxide particles and ytterbium trifluoride particles are used simultaneously.

The aforementioned preferred amounts of film former a) and/or filler particles f) in compositions according to the invention relate to both single-component and multi-component, for example two-component, compositions and are (as stated) in each case based on the total mass of the composition. In multi-component systems, the total mass of the composition results from the sum of the masses of all the individual components of the composition.

• - R¹ bedeutet eine Methoxygruppe oder Phenylgruppe, vorzugsweise eine Methoxygruppe und/oder
• - L ist eine Alkylengruppe mit 2 oder 3 Kohlenstoffatomen, vorzugsweise mit 2 Kohlenstoffatomen und/oder
• - R⁴ und R⁵ sind jeweils eine Einfachbindung.

A composition according to the invention is preferred in which:

• - R ¹ represents a methoxy group or phenyl group, preferably a methoxy group and/or
• - L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms and/or
• - R ⁴ and R ⁵ are each a single bond.

• - R¹ ist eine Methoxygruppe und R⁴ und R⁵ sind jeweils eine Einfachbindung und L ist eine Alkylengruppe mit 2 oder 3 Kohlenstoffatomen, vorzugsweise mit 2 Kohlenstoffatomen.

The following particularly preferably applies to a composition according to the invention:

• - R ¹ is a methoxy group and R ⁴ and R ⁵ are each a single bond and L is an alkylene group having 2 or 3 carbon atoms, preferably 2 carbon atoms.

A composition according to the invention is preferred
for use as a dental adhesive,
and/or
for use as a component of a dental multi-component adhesive,
and/or
wherein the composition is a universal dental adhesive.

• I) Herstellen oder Bereitstellen der ein oder mehreren Filmbildner a) sowie Herstellen oder Bereitstellen von ein oder mehreren weiteren Bestandteilen vorzugsweise ausgewählt aus der Gruppe bestehend aus den Bestandteilen b), c), d), e), f), g) und h);
• II) Mischen der in Schritt I) hergestellten bzw. bereitgestellten Bestandteile, so dass die Zusammensetzung resultiert.

The invention also relates to a process for producing a composition according to the invention or preferably according to the invention (as defined above and in the claims), comprising the following steps:

• I) producing or providing one or more film formers a) and producing or providing one or more further components preferably selected from the group consisting of components b), c), d), e), f), g) and h);
• II) Mixing the components prepared or provided in step I) to form the composition.

• I) Herstellen oder Bereitstellen der ein oder mehreren Filmbildner a) sowie Herstellen oder Bereitstellen von ein oder mehreren weiteren Bestandteilen vorzugsweise ausgewählt aus der Gruppe bestehend aus den Bestandteilen b), c), d), e), f), g), h), i) und j);
• II) Verteilung der in Schritt I) hergestellten bzw. bereitgestellten Bestandteile auf mehrere Komponenten, wobei vorzugsweise die Bestandteile b) und c) auf andere Komponenten als der Bestandteil i) verteilt werden;
• III) jeweiliges separates Mischen der in Schritt II) auf die mehreren Komponenten verteilten Bestandteile, so dass die mehrkomponentige Zusammensetzung resultiert,
  • wobei vorzugsweise die ein oder mehreren Filmbildner a) und die Bestandteile b), c), d), e) und f) auf eine erste von zwei Komponenten verteilt werden und die Bestandteile g) und i), gegebenenfalls zusätzlich zusammen mit dem Bestandteil j), auf eine zweite von zwei Komponenten verteilt werden, so dass eine zweikomponentige Zusammensetzung resultiert.

In a related aspect, the invention also relates to a process for producing a preferably multi-component composition according to the invention (as defined above and in the claims), comprising the following steps:

• I) producing or providing one or more film formers a) and producing or providing one or more further components preferably selected from the group consisting of components b), c), d), e), f), g), h), i) and j);
• II) distribution of the components produced or provided in step I) to several components, preferably components b) and c) being distributed to components other than component i);
• III) separate mixing of the components distributed over the several components in step II) to form the multi-component composition,
  • wherein preferably the one or more film formers a) and the components b), c), d), e) and f) are distributed over a first of two components and the components g) and i), optionally additionally together with the component j), are distributed over a second of two components, so that a two-component composition results.

The meaning of the above-mentioned components a), b), c), d), e), f), g), h), i) and j) is that as stated above and in the claims for compositions according to the invention or preferably according to the invention.

In the case of the preparation of preferably inventive multicomponent compositions comprising one or more co-initiators according to component h), these co-initiators can be contained as desired in one of the components or divided into several components.

The invention also relates to a composition according to the invention or preferably according to the invention (as defined above and in the claims) for use in a method for surgical or therapeutic treatment of the human or animal body and/or for use in a diagnostic method carried out on the human or animal body,

• - direkten oder indirekten Restauration von Zähnen, und/oder
• - intraoralen Reparatur von Füllungen, Keramikverblendungen und/oder Vollkeramikrestaurationen, und/oder
• - Behandlung überempfindlicher Zahnhälse, und/oder
• - Versiegelung von dentalen Kavitäten vor Amalgamrestaurationen und/oder vor temporären Befestigungen, oder in einem therapeutischen Verfahren als
  • - dentales Universal-Adhäsiv und/oder
  • - Schutzlack für Glasionomer Zementfüllungen.

preferably for specific application
in a therapeutic procedure for

• - direct or indirect restoration of teeth, and/or
• - intraoral repair of fillings, ceramic veneers and/or all-ceramic restorations, and/or
• - Treatment of hypersensitive tooth necks, and/or
• - Sealing of dental cavities prior to amalgam restorations and/or temporary cementation, or in a therapeutic procedure as
  • - dental universal adhesive and/or
  • - Protective varnish for glass ionomer cement fillings.

A multicomponent composition according to the invention (as defined above and in the claims) is preferred for use in a therapeutic method for fixing root posts.

• I) Vorbereiten der zu behandelnden Zahnpartie,
  • vorzugsweise durch Präparation der zu behandelnden Zahnpartie mit rotierenden Instrumenten und/oder durch Reinigen der zu behandelnden Zahnpartie,
• II) Herstellen oder Bereitstellen einer erfindungsgemäßen oder bevorzugt erfindungsgemäßen Zusammensetzung (wie oben und in den Ansprüchen definiert),
• III) Applizieren der in Schritt II) hergestellten oder bereitgestellten Zusammensetzung auf die in Schritt I) vorbereitete zu behandelnde Zahnpartie.

Finally, the invention also relates to a method for the therapeutic treatment of teeth comprising the following steps:

• I) Preparation of the tooth area to be treated,
  • preferably by preparing the tooth area to be treated with rotating instruments and/or by cleaning the tooth area to be treated,
• II) producing or providing a composition according to the invention or preferably according to the invention (as defined above and in the claims),
• III) Applying the composition prepared or provided in step II) to the tooth area to be treated prepared in step I).

In step I) mentioned above, the tooth area to be treated is typically prepared according to the common rules of minimally invasive dentistry and, if necessary, is freed of debris.

Compositions according to the invention comprise or consist of one or more film formers selected from the group consisting of polymers whose repeat units are or comprise structural units according to formula (I) (as defined above and in the claims).

• - Bereitstellen oder Herstellen eines Copolymers der allgemeinen Formel (V)
  
• - Umsetzen des Copolymers der allgemeinen Formel (V) mit einer Verbindung der allgemeinen Formel (VI),
  
  sodass ein oder mehrere erfindungsgemäße Filmbildner resultieren (vorzugsweise Filmbildner wie sie vorstehend oder nachstehend als bevorzugt bezeichnet sind), wobei R¹, R⁴, R⁵, X und L jeweils unabhängig voneinander die in einem der auf die erfindungsgemäße Zusammensetzung gerichteten Ansprüche oder der vorstehenden bzw. nachstehenden Beschreibung angegebene Bedeutung haben, vorzugsweise eine als bevorzugt bezeichnete Bedeutung.

The invention also relates to a process for producing a composition according to the invention (as defined in the claims or disclosed in the present description). Preferred embodiments of compositions according to the invention apply accordingly to the process according to the invention, and vice versa. The process according to the invention is one with the following steps:

• - Providing or preparing a copolymer of the general formula (V)
  
• - reacting the copolymer of general formula (V) with a compound of general formula (VI),
  
  so that one or more film formers according to the invention result (preferably film formers as described above or below as preferred), where R ¹ , R ⁴ , R ⁵ , X and L each independently of one another have the meaning given in one of the claims directed to the composition according to the invention or in the above or below description, preferably a meaning described as preferred.

• Zur Herstellung der Filmbildner wird zunächst in einer Vorstufe ein (vorzugsweise alternierendes) Copolymer der allgemeinen Formel (V) (wie oben definiert) hergestellt durch Umsetzung
  • (i) einer oder mehrerer Verbindungen der allgemeinen Formel (III) mit R¹ = Alkoxygruppe mit 1 bis 10 Kohlenstoffatomen oder Phenylgruppe (wenn R¹ = Alkoxygruppe mit 1 bis 10 Kohlenstoffatomen, dann ist die Verbindung der Formel (III) ein Alkyl-Vinylether; wenn R¹ = Phenylgruppe, dann ist die Verbindung der Formel (III) Styrol), mit
  • (ii) einem cyclischen, einfach ungesättigten Anhydrid der allgemeinen Formel (IV), wobei R⁴ und R⁵ gleich oder verschieden und jeweils eine Einfachbindung oder eine Alkylengruppe mit insgesamt 1 bis 4 Kohlenstoffatomen sind.

The film formers intended as a composition according to the invention or as a component of a composition according to the invention can be prepared, for example, as follows:

• To prepare the film formers, a (preferably alternating) copolymer of the general formula (V) (as defined above) is first prepared in a precursor stage by reacting
  • (i) one or more compounds of the general formula (III) with R ¹ = alkoxy group with 1 to 10 carbon atoms or phenyl group (if R ¹ = alkoxy group with 1 to 10 carbon atoms, then the compound of the formula (III) is an alkyl vinyl ether; if R ¹ = phenyl group, then the compound of the formula (III) is styrene), with
  • (ii) a cyclic, monounsaturated anhydride of the general formula (IV), wherein R ⁴ and R ⁵ are the same or different and each represent a single bond or an alkylene group having a total of 1 to 4 carbon atoms.

The conversion of the above-mentioned reactants (III) and (IV) to the copolymer (V) is generally illustrated by the following simplified reaction scheme S1:

Preferably, the one or at least one of the several compounds of formula (III) is styrene, methyl vinyl ether or ethyl vinyl ether.

Preferably, the cyclic, monounsaturated anhydride of the general formula (IV) is maleic anhydride (compound of the formula (IV), where R ⁴ and R ⁵ each represent a single bond).

Particularly preferably, the one or at least one of the several compounds of the formula (III) is styrene or an alkyl vinyl ether having 1 to 10 carbon atoms in the alkyl group (R ¹ is accordingly an alkoxy group having 1 to 10 carbon atoms), very particularly preferably styrene, methyl vinyl ether or ethyl vinyl ether, and the cyclic, monounsaturated anhydride of the general formula (IV) to be reacted therewith is maleic anhydride.

To produce the film formers, a compound of the general formula (VI) is used as a reactant for the (preferably alternating) copolymer (V), where X is hydrogen (H) or methyl (CH ₃ ) and L is selected from the group consisting of alkylene groups with a total of 2 to 10 carbon atoms or forms a polyethylene glycol group or a polypropylene glycol group together with an adjacent oxygen atom. The following figures (synthesis scheme S2; repeating unit of a polyethylene glycol group (VII), repeating unit of a polypropylene glycol group (VIII)) serve for illustration purposes.

Formula (VII) illustrates a repeating unit of a polyethylene glycol group and formula (VIII) illustrates a repeating unit of a polypropylene glycol group. Formula (IX) shows an example compound in which L together with an adjacent oxygen atom forms a triethylene glycol group.

R1

ist eine Alkoxygruppe mit insgesamt 1 bis 10 Kohlenstoffatomen oder eine Phenylgruppe; vorzugsweise ist R¹ eine Methoxygruppe (Alkoxygruppe mit 1 Kohlenstoffatom) oder Phenylgruppe, vorzugsweise eine Methoxygruppe

R2 und R3

sind gleich oder verschieden und jeweils ausgewählt aus der Gruppe bestehend aus H und Strukturen der Formel (II)

mit

X

ist H oder CH₃

L

ist ausgewählt aus der Gruppe bestehend aus Alkylengruppen mit insgesamt 2 bis 10 Kohlenstoffatomen, oder bildet zusammen mit einem benachbarten Sauerstoffatom eine Polyethylenglycolgruppe oder Polypropylenglycolgruppe, vorzugsweise ist L eine Alkylengruppe mit 2 oder 3 Kohlenstoffatomen, vorzugsweise mit 2 Kohlenstoffatomen.

und

R4 und R5

sind gleich oder verschieden und jeweils eine Einfachbindung oder eine Alkylengruppe mit insgesamt 1 bis 4 Kohlenstoffatomen, vorzugsweise sind R⁴ und R⁵ jeweils eine Einfachbindung,

The (preferably alternating) copolymer of formula (V) and the compound of general formula (VI) are reacted to form a film former whose repeat units are or comprise structural units according to formula (I) (as defined above and in the claims). A simplified, exemplary synthesis scheme is given in Scheme (S2), wherein the structural units X, L and R ¹ to R ⁵ are each as defined above and in the claims:

R1

is an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group; preferably R ¹ is a methoxy group (alkoxy group with 1 carbon atom) or phenyl group, preferably a methoxy group

R2 and R3

are the same or different and each selected from the group consisting of H and structures of the formula (II)

with

X

is H or CH ₃

L

is selected from the group consisting of alkylene groups with a total of 2 to 10 carbon atoms, or forms together with an adjacent oxygen atom a polyethylene glycol group or polypropylene glycol group, preferably L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

and

R4 and R5

are the same or different and each represents a single bond or an alkylene group with a total of 1 to 4 carbon atoms, preferably R ⁴ and R ⁵ are each a single bond,

• R¹ ist eine Methoxygruppe (Alkoxygruppe mit 1 Kohlenstoffatom), R⁴ und R⁵ sind jeweils eine Einfachbindung, L ist eine Alkylengruppe mit 2 oder 3 Kohlenstoffatomen, vorzugsweise mit 2 Kohlenstoffatomen.

At the same time, the following is particularly preferred:

• R ¹ is a methoxy group (alkoxy group with 1 carbon atom), R ⁴ and R ⁵ are each a single bond, L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

For details on preferred syntheses, please refer to the synthesis examples below.

Preferably alternating copolymers of methyl vinyl ether and maleic anhydride (hereinafter also referred to as poly(methyl vinyl ether-alt-maleic anhydride)) with various average molecular weights are commercially available; the CAS number is 9011-16-9. Analogous (preferably alternating) copolymers such as poly(styrene-alt-maleic anhydride) can be prepared in a corresponding manner.

The invention is explained in more detail below using examples. The examples given below are intended to describe and explain the invention in more detail without limiting its scope.

Synthesis Examples 1 to 13 each relate to the preparation of a composition according to the invention, namely a film former which is suitable for use as a dental adhesive and for use in a single-component dental adhesive or in a component of a multi-component dental adhesive.

A) Synthesis Examples 1 to 13: Preparation of film formers (suitable for use as compositions according to the invention or as a component of such compositions)

Synthesis example 1:

In a 1 liter round-bottomed flask, hydroxyethyl methacrylate (HEMA; 0.32 mol; 41.68 g) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 130,000 Da), pyridine (150 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature.

The reaction solution thus obtained was stirred for 24 hours at 40 °C and then cooled down to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 121.84 g (86% of the theoretical yield) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 2:

In a 1 liter round-bottomed flask, hydroxyethyl methacrylate (HEMA; 0.32 mol; 41.68 g) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 216,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature.

The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 117.6 g (83% of D.) of a film former a) for compositions according to the invention in the form of a colorless, amorphous powder. The successful conversion was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 3:

In a 1 liter round-bottomed flask, hydroxypropyl methacrylate (HPMA; 0.32 mol; 46.14 g; isomer mixture, see below) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 130,000 Da), pyridine (150 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 118.37 (81% of D.) g of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

The HPMA used is a mixture of isomers (CAS 27813-02-1), with 2-HPMA (CAS 923-26-2) being the main isomer, but also containing 2-hydroxy-1-methylethyl methacrylate (CAS 4664-49-7).

Synthesis example 4:

In a 1 liter round-bottomed flask, hydroxypropyl methacrylate (HPMA; 0.32 mol; 46.14 g, isomer mixture, composition as in Synthesis Example 3) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a N ₂ stream and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 216,000 Da), pyridine (150 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature.

The reaction solution thus obtained was stirred for 24 h at 40 °C and then cooled down to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 112.82 (77% of D.) g of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 5:

In a 1 liter round-bottomed flask, 10-hydroxydecyl methacrylate (0.32 mol; 77.55 g) was dissolved in 250 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 130,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 142.75 g (80% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 6:

In a 1 liter round-bottomed flask, 10-hydroxydecyl methacrylate (0.32 mol; 77.55 g) was dissolved in 250 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then sequently kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 216,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml THF was added dropwise over 3 h at room temperature.

The reaction solution thus obtained was stirred for 24 h at 40 °C and then cooled down to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 128.54 g (72% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 7:

In a 1 liter round-bottomed flask, triethylene glycol monomethacrylate (0.32 mol; 69.84 g) was dissolved in 250 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 130,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1 M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 130.27 g (77% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 8:

In a 1 liter round-bottomed flask, triethylene glycol monomethacrylate (0.32 mol; 69.84 g) was dissolved in 250 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 216,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature.

The reaction solution thus obtained was stirred for 24 h at 40 °C and then cooled down to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 126.36 g (74% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 9:

In a 1 liter round-bottomed flask, hydroxyethyl methacrylate (0.29 mol; 38.24 g) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(ethyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 160,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 106.17 g (79% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 10:

In a 1 liter round-bottomed flask, hydroxyethyl methacrylate (0.25 mol; 32.54 g) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(styrene-alt-maleic anhydride) (100 g; Mw = 135,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 112.30 g (85% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 11:

In a 1 liter round-bottomed flask, hydroxypropyl methacrylate (0.25 mol; 36.05 g; isomer mixture, composition as in synthesis example 3) was dissolved in 200 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(styrene-alt-maleic anhydride) (100 g; Mw = 135,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 77.55 g (57% of dry matter) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 12:

In a 1 liter round-bottomed flask, 10-hydroxydecyl methacrylate (0.25 mol; 60.59 g) was dissolved in 250 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(styrene-alt-maleic anhydride) (100 g; Mw = 135,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase in a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 105.57 g (66% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

Synthesis example 13:

In a 1 liter round-bottomed flask, triethylene glycol monomethacrylate (0.25 mol; 54.56 g) was dissolved in 250 ml of THF at room temperature. The solution was degassed for 30 min under a stream of N ₂ and then kept under a N ₂ atmosphere. A solution of poly(styrene-alt-maleic anhydride) (100 g; Mw = 135,000 Da), pyridine (10 ml) and 4-dimethylaminopyridine (0.05 mol; 6.25 g) in 250 ml of THF was added dropwise over 3 h at room temperature. The resulting reaction solution was stirred for 24 h at 40 °C and then cooled to room temperature. The solvent was removed under reduced pressure. The residue obtained was taken up in dichloromethane (400 ml) and washed with 0.1M HCl (3x 400 ml). The organic phase was separated from the aqueous phase using a separating funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 106.96 g (69% of D.) of a film former a) for compositions according to the invention were obtained in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

B) Preparation of compositions according to the invention and further investigations

Film formers according to synthesis examples 1 to 13 were used as functional components of compositions according to the invention. The compositions according to the invention were investigated with regard to the properties of shear bond strength and storage stability, in comparison with a non-inventive composition. The investigations carried out show the person skilled in the art how he can arrive at compositions with specific product properties by means of simple variations of components and their proportions.

In detail:

C) Preparation of test compositions based on synthesis examples 1 to 13:

Monomers, film formers, initiators, co-initiators, inhibitors and solvents were weighed in the proportions given in Tables 2 to 6, combined and stirred at room temperature for four hours until the solids were completely dissolved. The fillers were then added as an organic dispersion and the solvent was removed under reduced pressure. Finally, the solvents were added and stirred at room temperature for 30 minutes. Compositions were obtained, namely compositions according to the invention for use as a dental adhesive (Examples 2 to 30) or a non-inventive comparative composition (Example 1). The compositions used in the examples are also referred to below as test compositions or adhesives.

The compositions used in the examples are single-component; however, analogous results were also obtained with multi-component compositions.

D) Testing of shear bond strength

The test compositions obtained were each subjected to a shear test. The shear bond strength tests were carried out in accordance with ISO 29022:2013 - Dentistry - Adhesion - Shear bond strength test using a recessed blade, unless otherwise stated.

• Rinderfrontzähne wurden in eine Epoxid-Matrix in Form eines Rings mit Durchmesser d = 2,5 cm eingebettet und die Dentinfläche exponiert.

Details can be found in the following text:

• Bovine anterior teeth were embedded in an epoxy matrix in the form of a ring with a diameter of d = 2.5 cm and the dentin surface was exposed.

The surface of the teeth was standardized by rough grinding with P120 sandpaper with an average grain size of (125 +- 1 µm) and then fine grinding with P400 sandpaper with an average grain size of (35 +-1 µm). The tooth surface prepared in this way was cleaned of impurities under running deionized water and then freed of excess water by a short blast of air or by gently dabbing with a paper towel. The teeth were not overdried, so that morphological changes in the tooth hard substance were prevented.

The respective test composition (the respective adhesive) was applied to the prepared tooth surface and massaged into the surface for 20 seconds. The solvents contained in the test composition (in the adhesive) were removed by blasting with oil- and water-free compressed air for 5 seconds and then light-curing was carried out for 10 seconds (Celalux 2, 420 - 490 nm, 1000 W/cm ² ).

After the adhesive layer had hardened, the embedded tooth specimen was placed in a composite screw clamp including an insert mold (made of ISO 29022:2013 - Ultradent Products, South Jordan) was inserted.

The filling cavity of the insert mold was placed on the surface of the tooth and checked for adequate fit. The appliance was then fixed in place with screws.

Insertion of the composite into the cavity of the insert mold: The composite (GrandioSO A1, manufacturer: VOCO GmbH, Cuxhaven) was applied to the bonding surface using a suitable tamping instrument (composite tamper) and a tight contact was established without air bubbles. After filling the cylindrical part of the insert mold, the composite was light-cured for 20 s (Celalux 2, 420 - 490 nm, 1000 W/cm ² ). To avoid stresses that could have a negative effect on the adhesive bond (tension, torsion, shear, etc.), the composite test specimen equipped with a composite cylinder was carefully removed from the insertion mold and the clamping device.

The composite specimen was transferred to a specimen holder and clamped in place. A fixation for the recessed shear blade (crosshead construction with recessed blade) was installed in a universal testing machine (Zwick, Roell). The composite specimen, locked in its holder, was aligned in the holder under the crosshead with recessed blade, centered on the composite cylinder and the tooth, and positioned so that the recess in the crosshead and the composite cylinder to be sheared slid into each other without generating stress.

E) Storage stability

The test compositions were also subjected to accelerated aging at 50 °C and the time until noticeable gelation or polymerization occurred was recorded. The test compositions were divided into the following four groups depending on the gelation or polymerization that occurred.
“+++” Gelation or polymerization only after more than 3 months
“++” Gelation or polymerization after 1 to 3 months
“+” Gelation or polymerization after 7 days to 1 month
“0” gelation or polymerization in less than 7 days

For use as a dental adhesive, compositions are preferred which do not gel or polymerize at all or only after several months under the conditions of accelerated aging. For the purposes of the present task, test compositions with a rating of "+++" are therefore preferred, while those with a rating of "0" are least preferred.

F) Results

The components of the compositions investigated as well as the shear bond strength values and storage stabilities at 50 °C are listed below in Tables 2 to 6: The abbreviations used in Tables 2 to 6 are summarized in Table 1. Table 1 function abbreviation CAS No. substance monomer MDP 85590-00-7 10-Methacryloyloxydecyl phosphate monomer BisGMA 1565-94-2 2,2-Bis[4-methacryloyloxypolyethoxy-phenyl]propane monomer TEGDMA 109-16-0 triethylene glycol dimethacrylate monomer HEMA 868-77-9 2-hydroxyethyl methacrylate initiator CQ 10373-78-1 DL-camphorquinone co-initiator EDB 10287-53-3 4-(Dimethylamino)benzoic acid ethyl ester inhibitor BHT 128-37-0 2,6-Di-tert-butyl-4-methylphenol

In the example compositions according to Table 2 (Examples 2 to 6), the proportions of the film former (prepared according to the inventive synthesis example 1) and the proportions of the monomer BisGMA were varied. As can be seen from Table 2, the shear bond strength increases with increasing amount of the film former from the inventive synthesis example 1. In Example 5, a slight decrease and in Example 6 a greater decrease in the shear bond strength can be observed, which is probably due to the increasing proportion of the film former of 10 wt.% in Example 5 and 12 wt.% in Example 6. The storage stability also decreases slightly in Examples 5 and 6, ie from a proportion of 10.00 wt.% of the film former from the inventive synthesis example 1.

In the examples according to Table 3, the proportions of the monomer BisGMA and the filler silicon dioxide (SiO ₂ ) were varied. In Examples 11 and 12 of Table 3, a decrease in storage stability can be observed, which is probably due to the higher proportion of 8.00 wt.% SiO ₂ in Example 11 and 10.00 wt.% SiO ₂ in Example 12. The shear bond strength, however, is higher in Examples 11 and 12 than in the non-inventive Example 1 from Table 2. The highest shear bond strength in Table 3 is achieved in Example 10 with 29.80 wt.% BisGMA and 6.00 wt.% SiO ₂ .

In the example compositions according to Table 4, the proportions of the monomer BisGMA and the filler ytterbium trifluoride (YbF ₃ ) were varied. Example 17 has the highest proportion of YbF ₃ in Table 4 at 18.00 wt.% and has the lowest shear bond strength in Table 4. However, the shear bond strength of Example 17 can also be considered advantageous compared to Example 1, which is not according to the invention.

Example 18 has the highest shear bond strength of all the test compositions investigated, at 34.61 MPa. The high shear bond strength in Example 18 is probably due to the occurrence of a synergistic effect when silicon dioxide particles (SiO ₂ ) and ytterbium trifluoride particles (YbF ₃ ) are used simultaneously as filler particles.

In the example compositions according to Table 5, the type of film former was varied according to the inventive synthesis examples 2 to 7. In particular, the example composition 19, in which a film former according to synthesis example 2 (prepared with poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 216,000 Da) and hydroxyethyl methacrylate) showed not only a high shear bond strength but also a very good storage stability. The example compositions 21 and 22 with film formers according to the synthesis examples 4 (prepared with hydroxypropyl methacrylate and poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 216,000 Da)) and synthesis example 5 (prepared with 10-hydroxydecyl methacrylate and poly(methyl vinyl ether-alt-maleic anhydride) (100 g; Mw = 130,000 Da)) also showed very good shear bond strengths and particularly good storage stability.

In the example compositions according to Table 6, the type of film former was varied according to the inventive synthesis examples 8 to 13. From Examples 25 and 27 it can be seen that film formers made with poly(ethyl vinyl ether-alt-maleic anhydride) (used in synthesis example 9) and film formers made with poly(styrene-alt-maleic anhydride) (used in synthesis example 10) also show sufficient storage stability and shear bond strengths in the example compositions. Examples 28 to 30 showed lower storage stability, but the shear bond strengths were also better here than in non-inventive example 1 from Table 2.

QUOTES INCLUDED IN THE DESCRIPTION

This list of documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions.

Cited non-patent literature

• Systematic review of the chemical composition of contemporary dental adhesives” by Van Landuyt et al. in Biomaterials 28(2007) 3757-3785 [0004]
• Looking for the ideal adhesive - A review” by Sezinando in Revista Portuguesa de Estomatologia, Medicina Dentaria e Cirurgia Maxilofacial, 2014, 55(4): 194-206 [0004]
• Classification review of dental adhesive systems: from the IV generation to the universal type” by Sofan et al. in Annali di stomatologia, 2017, VIII(1):1-17 [0004]
• 10-MDP Based Dental Adhesives: Adhesive Interface Characterization and Adhesive Stability - A Systematic Review” by Carrilho et al. in Materials, 2019, 12, 790 [0004]
• ISO 29022:2013 [0113]

Claims (20)

Composition comprising or consisting of a) one or more film formers selected from the group consisting of polymers whose repeating units are or comprise structural units according to formula (I)

where R ¹ , R ² , R ³ , R ⁴ and R ⁵ in each structural unit independently of one another: R ¹ represents an alkoxy group having a total of 1 to 10 carbon atoms or a phenyl group, R ² and R ³ are the same or different and are each selected from the group consisting of H and structures of the formula (II)

where X is H or CH ₃ and L is selected from the group consisting of alkylene groups having a total of 2 to 10 carbon atoms or forms together with an adjacent oxygen atom a polyethylene glycol group or a polypropylene glycol group and R ⁴ and R ⁵ are the same or different and each represent a single bond or an alkylene group having a total of 1 to 4 carbon atoms, the composition being suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive. Composition according to claim 1 , additionally comprising as one or more further components: b) as adhesion promoter one or more polymerizable monomers, wherein the one or more polymerizable monomers of component b) have one or more acidic functional groups, and/or c) one or more further polymerizable monomers, wherein the one or more further polymerizable monomers of component c) are different from the one or more polymerizable monomers of component b) and are selected from the group consisting of acrylates, methacrylates, acrylamides and methacrylamides, and/or d) one or more photoinitiators, and/or e) one or more inhibitors, and/or f) as filler non-aggregated and non-agglomerated filler particles with a particle size in the range of 7 to 70 nm, wherein the filler particles are silicon dioxide particles and/or ytterbium trifluoride particles, and/or g) one or more solvents, preferably one or more solvents selected from the group consisting of water, ethanol, isopropanol and acetone, and/or h) one or more co-initiators, preferably selected from the group consisting of amines and boranes, particularly preferably selected from the group consisting of tertiary amines. Composition according to claim 2 , wherein the one or more further polymerizable monomers of component c) are each either monofunctional or oligofunctional, and/or amphiphilic or hydrophobic. Composition according to claim 2 or 3 , wherein the filler particles of component f) are surface-modified, and/or the particle size of the filler particles of component f) is in the range from 10 to 15 nm for silicon dioxide particles and/or in the range from 7 to 60 nm for ytterbium trifluoride particles, preferably in the range from 7 to 50 nm, particularly preferably in the range from 20 to 40 nm. Composition according to one of the Claims 2 until 4 , wherein the ratio of the total mass of component c) to the total mass of the one or more film formers a) is in the range from 4.5:1 to 96:1, preferably in the range from 10:1 to 15:1, and/or the ratio of the total mass of component c) to the total mass of component f) is in the range from 2.25:1 to 96:1, preferably in the range from 3:1 to 6:1, and/or the ratio of the total mass of the one or more film formers a) to the total mass of component f) is in the range from 1:20 to 10:1, preferably in the range from 1:3 to 1:1. Composition according to one of the preceding claims, preferably according to one of the Claims 2 until 5 , comprising the one or more film formers a) in an amount of up to 10 percent by weight, preferably in an amount in the range from 1 to 10 percent by weight, particularly preferably in an amount in the range from 2 to 8 percent by weight, and/or the component b) in an amount in the range from 1 to 5 percent by weight, and/or the component c) in an amount in the range from 45 to 79 percent by weight, and/or the component d) in an amount in the range from 0.1 to 3.5 percent by weight, preferably in the range from 0.1 to 1.5 percent by weight, and/or the component e) in an amount in the range from 0.01 to 0.5 percent by weight, and/or the component f) in an amount in the range from 1 to 20 percent by weight, and/or the component g) in an amount in the range from 7.5 to 35 percent by weight, preferably in the range from 10 to 27.5 percent by weight, particularly preferably in the range of 15 to 25 percent by weight, very particularly preferably in the range of 17.5 to 20 percent by weight, and/or component h) in an amount in the range of 0.1 to 2 percent by weight, in each case based on the total mass of the composition. Composition according to one of the Claims 1 until 5 , wherein the composition is multi-component, wherein the composition preferably comprises as a further component i) initiators for chemical curing, particularly preferably for chemical curing at ambient temperature, wherein the one or more initiators of component i) are different from the one or more photoinitiators of component d), and wherein components b) and c), preferably components b), c) and the one or more film formers a), are present separately from component i), preferably separately from components g) and i). Composition according to claim 7 , wherein the composition is two-component, consisting of - a first component comprising the one or more film formers a) and the components b), c), d), e) and f), and - a second component comprising the components g) and i), wherein the first and the second component are each present as separate individual components. Composition according to claim 8 , wherein component g) is contained in the second component in an amount in the range from 50 to 99 percent by weight, preferably in the range from 80 to 98 percent by weight, based on the total mass of the second component, and/or the one or more initiators of component i) are selected from the group consisting of peroxides, redox initiators and initiators for chemical, non-radiative curing, preferably selected from the group consisting of sulfinates and borates and particularly preferably selected from the group consisting of sodium toluene sulfinate and four-coordinated borates, and/or component i) is contained in the second component in an amount in the range from 0.1 to 10 percent by weight, preferably in the range from 1 to 5 percent by weight, based on the total mass of the second component, and/or the second component comprises as additional component j) one or more solubilizers, preferably 2-butanone, wherein component j) in the second component preferably in an amount in the range from 0.1 to 2 percent by weight, based on the total mass of the second component. Composition according to one of the Claims 8 or 9 , wherein the first component comprises one or more film formers a) in an amount in the range of 1 to 10 percent by weight, and/or comprises component b) in an amount in the range of 1 to 5 percent by weight, and/or comprises component c) in an amount in the range of 45 to 96 percent by weight, and/or comprises component d) in an amount in the range of 0.1 to 1.5 percent by weight, and/or comprises component e) in an amount in the range of 0.01 to 0.5 percent by weight, and/or comprises component f) in an amount in the range of 1 to 20 percent by weight, in each case based on the total mass of the first component. Composition according to one of the preceding claims, preferably according to one of the Claims 2 until 10 , comprising the one or more film formers a) in an amount in the range of 5 to 8 percent by weight, preferably in the range of 6 to 8 percent by weight, and/or the component f) in an amount in the range of 2 to 15 percent by weight, preferably in the range of 5 to 12 percent by weight, particularly preferably in the range of 6 to 8 percent by weight, in each case based on the total mass of the composition. Composition according to one of the Claims 2 until 11 , wherein the filler particles of component f) are silicon dioxide particles and component f) is contained in the composition in an amount in the range of 2 to 8 percent by weight, preferably in the range of 5 to 6 percent by weight, based on the total mass of the composition, or the filler particles of component f) are ytterbium trifluoride particles and component f) is contained in the composition in an amount in the range of 12 to 15 percent by weight, based on the Total mass of the composition, or component f) consists of 2 to 4 percent by weight of silicon dioxide particles and 2 to 4 percent by weight of ytterbium trifluoride particles, preferably of 3 percent by weight of silicon dioxide particles and 3 percent by weight of ytterbium trifluoride particles, each based on the total mass of the composition. Composition according to one of the preceding claims, wherein: - R ¹ is a methoxy group or phenyl group, preferably a methoxy group and/or - L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms and/or - R ⁴ and R ⁵ are each a single bond, wherein preferably: - R ¹ is a methoxy group and R ⁴ and R ⁵ are each a single bond and L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms. Composition according to one of the preceding claims, for use as a dental adhesive, and/or for use as a component of a multi-component dental adhesive, and/or wherein the composition is a universal dental adhesive. Process for preparing a composition according to one of the Claims 1 until 6 or 11 until 14 , comprising the following steps: I) producing or providing the one or more film formers a) and producing or providing one or more further components, preferably selected from the group consisting of components b), c), d), e), f), g) and h); II) mixing the components produced or provided in step I) to result in the composition. Process for the preparation of a multicomponent composition according to one of the Claims 7 until 14 , comprising the following steps: I) producing or providing the one or more film formers a) and producing or providing one or more further components, preferably selected from the group consisting of components b), c), d), e), f), g), h), i) and j); 11) distribution of the components produced or provided in step I) over several components, wherein preferably components b) and c) are distributed over components other than component i); III) separate mixing of the components distributed over the several components in step II) so that the multi-component composition results, wherein preferably the one or more film formers a) and components b), c), d), e) and f) are distributed over a first of two components and components g) and i), optionally additionally together with component j), are distributed over a second of two components so that a two-component composition results. Composition according to one of the Claims 1 until 14 for use in a method for surgical or therapeutic treatment of the human or animal body and/or for use in a diagnostic method performed on the human or animal body, preferably for specific use in a therapeutic method for - direct or indirect restoration of teeth, and/or - intraoral repair of fillings, ceramic veneers and/or all-ceramic restorations, and/or - treatment of hypersensitive tooth necks, and/or - sealing of dental cavities before amalgam restorations and/or before temporary fixings, or in a therapeutic procedure as - a universal dental adhesive and/or - a protective varnish for glass ionomer cement fillings. Composition according to one of the Claims 7 until 14 for use in a therapeutic procedure for the fixation of root posts. Method for the therapeutic treatment of teeth comprising the following steps: I) preparing the tooth area to be treated, preferably by preparing the tooth area to be treated with rotating instruments and/or by cleaning the tooth area to be treated, II) producing or providing a composition according to one of the Claims 1 until 14 , III) Applying the composition prepared or provided in step II) to the tooth area to be treated prepared in step I). Process for preparing a composition according to one of the Claims 1 until 14 , comprising the following steps: - Providing or preparing a copolymer of the general formula (V)

- reacting the copolymer of general formula (V) with a compound of general formula (VI),

so that one or more film formers result, as in one of the Claims 1 until 14 where R ¹ , R ⁴ , R ⁵ , X and L each independently represent the Claims 1 until 14 have the meaning specified.