Composition for use as a dental adhesive or for use as a component of a multi-component dental adhesive, as well as preparation method and applications

Abstract

The 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 invention also relates to a method for preparing a composition according to the invention. The invention additionally relates to a composition according to the invention for application in a method for treatment of the human or animal body by surgery or therapy and / or for application in a diagnostic method carried out on the human or animal body. The invention also relates to a method for treating teeth by therapy.

Description

[0001] Composition for use as a dental adhesive or for use as a component of a multi-component dental adhesive, as well as manufacturing processes and applications

[0002] 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 additionally relates to a composition according to the invention for use in a method for the 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 further emerge from the following description, including the examples.

[0003] To the extent that 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 regarding 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 otherwise apparent to the person skilled in the art from the present text in the individual case.

[0004] Compositions for use as dental adhesives are already known from the state of the art and are described, for example, in the following publications:

[0005] (1 ) „Systematic review of the chemical composition of contemporary dental adhesives“ von Van Landuyt et al. in Biomaterials 28(2007) 3757-3785;

[0006] (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;

[0007] (3) „Classification review of dental adhesive systems: from the IV generation to the universal type” on Sofan et al. in Annali di stomatologia, 2017, Vlll(1):1 -17;

[0008] (4) „10-MDP Based Dental Adhesives: Adhesive Interface Characterization and Adhesive Stability - A Systematic Review” von Carrilho et al. in Materials, 2019, 12, 790.

[0009] Compositions for use as dental adhesives are used in dentistry, particularly for bonding filling materials or dentures to the tooth (dentin). Since dental restorations generally aim to achieve a permanent and firm bond between the tooth and the filling material or denture, which must primarily withstand the mechanical stresses that occur regularly (e.g., during 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.

[0010] 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 - Recessed blade shear bond strength test), in particular for the application field of bonding dentin (biological tooth material) with dental restorations and dental composites (synthetic dental fillings, etc.) under light curing.Furthermore, the composition to be provided should preferably enable the achievement of a high quality for the hybrid layer formed after application of the composition to the tooth (for the term "hybrid layer," see the above-mentioned publication (4), Carrilho et al., page 12, last full paragraph). Furthermore, 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 perspective.

[0011] The composition to be specified should, in addition to excellent shear bond strength, preferably also have excellent storage stability.

[0012] 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.

[0013] Furthermore, the invention should take into account that the composition to be provided is suitable for use in a method for the surgical or therapeutic treatment of the human or animal body and / or for use in a diagnostic method which 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 fixing.

[0014] Further tasks and associated technical effects emerge from the following description and the patent claims.

[0015] The primary object of the present invention is achieved by a 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)

[0016] where for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other:

[0017] R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0018] R 2 and R 3 are the same or different and are each selected from the group consisting of H and structures of formula (II) (II), with

[0019] X is H or CH3 and

[0020] 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

[0021] 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

[0022] R 4 and R 5 are the same or different and each represent a single bond or an alkylene group with a total of 1 to 4 carbon atoms, wherein preferably R 4 and R 5 have in total not more than 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.

[0023] Preferably, R 1a methoxy group (alkoxy group with 1 carbon atom) or phenyl group, preferably a methoxy group.

[0024] Preferably, R 4 and R 5 a single bond each.

[0025] Preferably, L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms.

[0026] At the same time, the following are particularly preferred:

[0027] 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.

[0028] Structures of formula (II) are preferably suitable for radical polymerization with each other and / or with other components of the composition. They are preferably intended for radical polymerization. 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.

[0029] A composition consisting of a) several film formers is a mixture of two or more such film former polymers.

[0030] 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.

[0031] The use of film-forming agents in compositions for use as dental adhesives or for use as components of a multi-component dental adhesive primarily improves 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-forming agents defined above results in an excellent surface quality, which is often perceived as improved in direct comparison with film-forming agents known from the prior art. The skilled person often evaluates the surface quality by considering or determining one or more of the following properties:

[0032] Flow behavior: This is influenced by the film-forming agent and describes the interaction between the surface and the adhesive through attractive or repulsive forces. The most common measurement of this parameter is the contact angle. A very small contact angle to the substrate is generally advantageous; an applied adhesive then already has strong contact with the surface due to physical phenomena.

[0033] Homogeneity of the resulting surface: The adhesive film is formed by evaporation of the volatile components (e.g., solvents) of typical compositions used as dental adhesives. This involves the application of force and thus movement of the liquid composition. Since viscosity generally increases during evaporation, perfect leveling of the surface of the resulting film is not always achieved. Poor-quality films or layers are topographically characterized by "peaks and valleys," craters, and the like. Such inhomogeneities introduce potential defect sites into the dental restoration during the application and drying steps of 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 manifestation of disturbing topographical structures (as described above) when the volatile components evaporate, compared with the prior art.

[0034] Initial tack / grip: In a conventional composite buildup, a small amount of material is transferred to the applied adhesive film using dental tools. A ready release of the composite from the tool is desirable. To achieve this, the physical shear bond strength between the adhesive composition and the composite (initial tack / 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 multi-component dental adhesive is advantageous in this regard.

[0035] 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 of the corresponding compositions, but also causes a significant increase in the shear bond strength of corresponding compositions according to the invention.

[0036] The number of structural units according to formula (I) in the macromolecules of the (film-forming) polymer is preferably 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.

[0037] 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.

[0038] The "snake line" (^ ) contained in formula (II) expresses that the unit designated by the letter "L" is linked via a covalent bond to the structural unit according to formula (I), i.e. in the case of the structure according to formula (II) it is linked via a covalent bond to the oxygen atom, which in the general formula (I) is bonded to the unit "R 2 “ and / or is connected via a covalent bond to the oxygen atom, which in the general formula (I) forms a bond to the element “R 3 “ trained.

[0039] A composition according to the invention is preferably 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 (preferably "and", ie both b and c) 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 referred to as stabilizers), 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 (SiO2) particles and / or ytterbium trifluoride (YbF3) 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,

[0040] The one or more acidic functional groups of the one or more polymerizable monomers of component b) contribute to a preferably acidic pH in corresponding compositions. A composition according to the invention with a pH in the range of 1 to 4.5 is preferred. The one or at least one of the several polymerizable monomers of component b) is preferably radically polymerizable and / or suitable for radical reaction with other components of the composition, preferably for radical reaction with structures of formula (II).

[0041] The one or more further 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 cohesive strength, degree of linkage of the resulting polymer network, flexibility, etc., are all controlled by the choice of the polymer matrix. The one or at least one of the several polymerizable monomers of component c) is preferably radically polymerizable and / or suitable for radical reaction with other components of the composition, preferably for radical reaction with structures of formula (II) and / or with radically polymerizable monomers of component b).

[0042] The one or more photoinitiators of component d) in appropriate compositions enable light curing and the processing speeds typical in modern dentistry; due to the presence of photoinitiators, polymerization can be carried out in a short time. The one or more inhibitors (also called stabilizers) of component e) in appropriate compositions contribute to achieving sufficient storage stability. Due to their high affinity for radicals, they form stable reaction products with them, thus preventing premature (often thermal) polymerization processes.

[0043] 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) results in a structure-reinforcing effect, so that, for example, a (further) shift in the cohesive fracture limit to higher values ​​can be achieved by using non-aggregated and non-agglomerated filler particles according to component f). The use of ytterbium trifluoride particles also advantageously leads to an increase in radiopacity, so that, when using ytterbium trifluoride particles, a dentin-like radiopacity can preferably be achieved.

[0044] The particle size distribution of the non-aggregated and non-agglomerated filler particles of component f) is preferably determined by dynamic light scattering, for example, using 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 obtained data for the volume-weighted particle size distribution are evaluated and displayed, for example, using the ZetaSizer software V7.13. A particle size, within the meaning of the present invention, is understood to mean the d50 values ​​thus obtained from volume-weighted evaluation.

[0045] A preferred composition according to the invention preferably 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).

[0046] The solvents according to component g) often serve, in particular, to compatibilize the other ingredients, to homogenize, and to influence the flow behavior. Acting on the tooth, they can stabilize the exposed collagen fibers during resin infiltration. Due to the higher vapor pressure of the organic solvents, they facilitate the removal of 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 present in any one, several, or all components. Co-initiators act as radical carriers. For example, the initiator camphorquinone cannot satisfactorily transfer its excited state to the unsaturated substrates on its own.Co-initiators can be viewed as mediators that form reactive radicals upon fluorine abstraction of the excited camphorquinone, which are then readily transferred to the substrates. Camphorquinone / amine synergism is a classic example of the interplay between initiator and co-initiator, and is well described in the relevant literature.

[0047] 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.

[0048] The selection of functionality is crucial for determining 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.

[0049] 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.

[0050] 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) 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.

[0051] In comparative screenings of compositions according to the invention in which the said non-aggregated and non-agglomerated filler particles with the said preferred particle sizes were used, a particularly high shear bond strength was obtained.

[0052] The ytterbium trifluoride particles are preferably surface-modified with methacryloylphosphoric acid or a derivative thereof, particularly preferably with MDP. MDP denotes 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 denotes [3-(methacryloyloxy)propyl]trimethoxysilane (CAS No. 2530-85-0).

[0053] A composition according to the invention is preferred in which 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 ratios mentioned are set, convince in comparative tests due to the high shear bond strength achieved.

[0054] 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 in the range from 1 to 5 percent by weight, and / or component c) in an amount in the range from 45 to 79 percent by weight, and / or 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 component e) in an amount in the range from 0.01 to 0.5 percent by weight, and / or component f) in an amount in the range from 1 to 20 percent by weight, and / or 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.

[0055] The adjustment of the aforementioned preferred ratios and / or proportions advantageously leads to compositions according to the invention having a particularly high shear bond strength.

[0056] A composition according to the invention is preferred, 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).

[0057] The particularly preferred composition thus comprises components b), c), d) and e) as defined above and in the appended claims, and additionally the initiators of component i).

[0058] 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. "Separate" means, for the aforementioned components or groups of components of the multi-component composition within the meaning of the present invention, that they are contained in different, spatially separated components of the multi-component composition.

[0059] 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.

[0060] Further preferred is a multi-component composition according to the invention, wherein the composition is two-component, consisting of

[0061] - a first component comprising the one or more film formers a) and the components b), c), d), e) and f) as defined above and in the appended claims and

[0062] - a second component comprising the components g) and i) as defined above and in the appended claims, wherein the first and the second component are each present as separate individual components (ie spatially separated from one another).

[0063] The advantages of spatial separation outlined above apply accordingly. Preferably, measures are taken to design the second component so that it is stable in itself and can be easily mixed with the first component. To this extent, the second component is preferably designed so that the solvent(s) of component g) is / are inert toward the one or more initiators of component i).

[0064] Also preferred is a multi-component composition according to the invention, wherein component g) is present 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-coordinate borates, and / or component i) is present 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 additional component j) one or more solubilizers, preferably 2-butanone, wherein component j) is preferably present 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.

[0065] In the context of the present invention, the term "nonradiative" means that the corresponding initiators are suitable for curing without the external influence of radiation. Therefore, light irradiation is not absolutely necessary when using initiators for chemical, nonradiative curing.

[0066] Also preferred is a multi-component composition according to the invention, wherein the first component comprises one or more film formers a) in an amount in the range from 1 to 10 percent by weight, and / or comprises component b) in an amount in the range from 1 to 5 percent by weight, and / or comprises component c) in an amount in the range from 45 to 96 percent by weight, and / or comprises component d) in an amount in the range from 0.1 to 1.5 percent by weight, and / or comprises component e) in an amount in the range from 0.01 to 0.5 percent by weight, and / or comprises component f) in an amount in the range from 1 to 20 percent by weight, in each case based on the total mass of the first component.

[0067] The adjustment of the above-mentioned 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.

[0068] A composition according to the invention, preferably a preferred composition according to the invention, as defined above or below, is preferred, comprising the one or more film formers a) in an amount in the range from 5 to 8 percent by weight, preferably in the range from 6 to 8 percent by weight, and / or the component f) in an amount in the range from 2 to 15 percent by weight, preferably in the range from 5 to 12 percent by weight, particularly preferably in the range from 6 to 8 percent by weight, in each case based on the total mass of the composition.

[0069] Also preferred is a composition according to the invention wherein the filler particles of component f) are silicon dioxide particles and component f) is present in the composition in an amount in the range from 2 to 8 percent by weight, preferably in the range from 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 present in the composition in an amount in the range from 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, in each case based on the total mass of the composition.

[0070] It has been shown that the aforementioned preferred amounts of film former a) and / or filler particles f) in compositions according to the invention have a particularly advantageous effect on the level of achievable shear bond strength. In particular, it was observed that the simultaneous use of both silicon dioxide particles and ytterbium trifluoride particles as filler particles f) significantly increases the shear bond strength, which can presumably be attributed to the occurrence of a synergistic effect when silicon dioxide particles and ytterbium trifluoride particles are used simultaneously.

[0071] The aforementioned preferred amounts of film former a) and / or filler particles f) in compositions according to the invention refer to both single-component and multi-component, for example two-component, compositions and are (as stated) 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 individual components of the composition. A preferred composition according to the invention is one in which the following applies:

[0072] R 1 means a methoxy group or phenyl group, preferably a methoxy group and / or

[0073] L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms and / or

[0074] R 4 and R 5 are each a single bond.

[0075] Particularly preferred for a composition according to the invention:

[0076] R 1 is a methoxy group and R 4 and R 5 are each a single bond and L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

[0077] 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 dental universal adhesive.

[0078] 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 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);

[0079] II) Mixing the components prepared or provided in step I) to produce the composition.

[0080] 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:

[0081] 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);

[0082] II) distribution of the components produced or provided in step I) among several components, wherein preferably components b) and c) are distributed among components other than component i);

[0083] III) separate mixing of the components distributed in step II) among the several components, so that the multi-component composition results, wherein preferably the one or more film formers a) and the components b), c), d), e) and f) are distributed among a first of two components and the components g) and i), optionally additionally together with the component j), are distributed among a second of two components, so that a two-component composition results.

[0084] 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.

[0085] In the case of the production of preferably inventive multi-component 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 can be distributed over several components. The invention also relates to an inventive or preferably inventive composition (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 which is carried out on the human or animal body, preferably for specific use in a therapeutic method for

[0086] - direct or indirect restoration of teeth, and / or

[0087] - intraoral repair of fillings, ceramic veneers and / or all-ceramic restorations, and / or

[0088] - Treatment of hypersensitive tooth necks, and / or

[0089] - Sealing of dental cavities before amalgam restorations and / or before temporary cementation, or in a therapeutic procedure as

[0090] - dental universal adhesive and / or

[0091] - 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 securing root posts.

[0092] Finally, the invention also relates to a method for the therapeutic treatment of teeth comprising the following steps:

[0093] 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,

[0094] II) Producing or providing a composition according to the invention or preferably according to the invention (as defined above and in the claims),

[0095] III) Applying the composition prepared or provided in step II) to the tooth area to be treated prepared in step I).

[0096] 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.

[0097] Compositions according to the invention comprise or consist of one or more film formers selected from the group consisting of polymers whose repeating units are or comprise structural units according to formula (I) (as defined above and in the claims).

[0098] 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 the 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 comprising the following steps:

[0099] Providing or preparing a copolymer of the general formula (V)

[0100] 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 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 designated as preferred.

[0101] 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:

[0102] To produce the film formers, a (preferably alternating) copolymer of the general formula (V) (as defined above) is first prepared in a precursor stage by reacting

[0103] (i) one or more compounds of general formula (III) with R 1 = alkoxy group with 1 to 10 carbon atoms or phenyl group (if R 1 = alkoxy group having 1 to 10 carbon atoms, then the compound of formula (III) is an alkyl vinyl ether; if R 1= phenyl group, then the compound of formula (III) is styrene), with

[0104] (ii) a cyclic monounsaturated anhydride of the general formula (IV), where R 4 and R 5 identical or different and each represent a single bond or an alkylene group with a total of 1 to 4 carbon atoms.

[0105] The conversion of the above-mentioned reactants (III) and (IV) to the copolymer (V) is generally illustrated by the following simplified reaction scheme S1:

[0106] Preferably, the one or at least one of the several compounds of formula (III) is styrene, methyl vinyl ether or ethyl vinyl ether.

[0107] 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).

[0108] Particularly preferably, the one or at least one of the several compounds of 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.

[0109] 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 (CH3) and L is selected from the group consisting of alkylene groups having a total of 2 to 10 carbon atoms or, together with an adjacent oxygen atom, forms a polyethylene glycol group or a polypropylene glycol group. 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.

[0110] 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.

[0111]

[0112] The (preferably alternating) copolymer of formula (V) and the compound of general formula (VI) are reacted to form a film former whose repeating units are or comprise structural units according to formula (I) (as defined above and in the claims). A simplified, exemplary synthesis scheme is shown in Scheme

[0113] (S2), where the structural units X, L and R 1 to R 5 each as defined above and in the claims:

[0114] R 1 is an alkoxy group with a total of 1 to 10 carbon atoms or a

[0115] Phenyl group; preferably R 1 a methoxy group (alkoxy group with 1 carbon atom) or phenyl group, preferably a methoxy group

[0116] R 2 and R 3are the same or different and are each selected from the group consisting of H and structures of formula (II) with

[0117] X is H or CH3

[0118] 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 polypropylene glycol group, preferably L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms. and

[0119] R 4 and R 5 are the same or different and each represent a single bond or an alkylene group with a total of 1 to 4 carbon atoms, preferably R 4 and R 5 a single bond each,

[0120] At the same time, the following are particularly preferred:

[0121] R 1 is a methoxy group (alkoxy group with 1 carbon atom), R 4 and R 5are each a single bond, L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

[0122] For details on preferred syntheses, please refer to the synthesis examples below.

[0123] 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.

[0124] A series of preferred compositions (i) to (vii) according to the invention are defined below. These preferred compositions are each particularly suitable and intended for use in a therapeutic method for securing root posts. They are also each particularly intended to be prepared or provided in a method according to the invention for the therapeutic treatment of teeth (step II) and to be applied in step (III). The preferred compositions are preferably prepared by a method according to the invention (as defined in the claims and described above) and are thus a preferred result of a manufacturing method according to the invention.The preferred compositions according to the invention (as defined above and below and in the claims) differ from one another in certain features; particularly preferred are compositions according to the invention in which the respective features of two or more preferred embodiments are combined.

[0125] Preferred compositions (i) to (vii) according to the invention:

[0126] (i) Preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims) comprising 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 for R 1 , R 2 , R 3 , R 4 and R 5in each structural unit independently of each other:

[0127] R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0128] R 2 and R 3 are the same or different and are each selected from the group consisting of H and structures of formula (II) (II), with

[0129] X is H or CH3 and

[0130] 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 and R 4 and R 5are the same or different and each represent a single bond or an alkylene group having a total of 1 to 4 carbon atoms, and additionally comprising: 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 (preferably “and”, ie both b and c) 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, wherein the composition is suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive.

[0131] If the preferred composition according to the invention comprises component b), the one or at least one of the several polymerizable monomers of component b) is preferably radically polymerizable and / or suitable for radical reaction with other components of the composition, preferably for radical reaction with structures of formula (II).

[0132] If the preferred composition according to the invention comprises component c), the one or at least one of the several polymerizable monomers of component c) is preferably radically polymerizable and / or suitable for radical reaction with further components of the composition, preferably for radical reaction with structures of the formula (II) and / or with radically polymerizable monomers of component b).

[0133] If the preferred composition according to the invention comprises components b) and c), preferably one or at least one of the several polymerizable monomers of component b) is radically polymerizable and / or suitable for radical reaction with other components of the composition, in particular for radical reaction with structures of the formula (II) and with radically polymerizable monomers of component c) and at the same time one or at least one of the several polymerizable monomers of component c) is radically polymerizable and / or suitable for radical reaction with other components of the composition, in particular for radical reaction with structures of the formula (II) and with radically polymerizable monomers of component b).

[0134] Due to the presence of components b) and / or c) (preferably both components b and c) in addition to component a) (i.e., in addition to the film formers), the preferred composition is particularly well suited to enabling a permanent bond between a filling, ceramic veneer, or all-ceramic restoration and the tooth substance. Since, when restoring teeth, the aim is generally to achieve a permanent and firm bond between the tooth and the filling material or dental prosthesis used, which must primarily withstand the mechanical stresses that occur regularly (e.g., due to 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.

[0135] By polymerizing the polymerizable monomers b) and c), a stable bond is created between the tooth structure and the filling, ceramic veneer, or all-ceramic restoration. The stability of the bond can be determined by measuring the shear bond strength: the higher the shear bond strength, the more stable the bond. For example, a comparison between Examples 10 (29.80 wt% BisGMA, shear bond strength 32.55 MPa) and 12 (25.80 wt% BisGMA, shear bond strength 24.16 MPa) shows that the shear bond strength decreases at lower concentrations of BisGMA (component c). The lower shear bond strengths in Examples 6 and 7 are due to the lower amounts of the filler SiO2 in the example compositions. For the influence of the filler on the shear bond strength, please refer to the following section (ii).

[0136] Particularly preferably, the preferred composition according to the invention also contains a photoinitiator in addition to components b) and / or c) (preferably in addition to both components b and c). Photoinitiators are preferred over other initiators due to their ease of use in dentistry (comprising illumination with a polymerization lamp). The one or at least one of the several, preferably all, polymerizable monomers each containing one or more acidic functional groups is or are preferably selected from the group consisting of polymerizable monomers containing acidic protons, phosphate groups, carboxylate groups, sulfate groups, and sulfite groups, as well as their anhydrides, which can be converted into the corresponding functional groups containing acidic protons by subsequent hydrolysis.

[0137] Particularly preferred is the one or at least one of the several, preferably all, polymerizable monomers each having one or more acidic functional groups selected from the group consisting of hydroxyethyl methacryloyl dihydrogen phosphate, hydroxypropyl methacryloyl dihydrogen phosphate, bis(methacryloyloxyethyl)hydrogen phosphate, bis(methacryloyloxypropyl)hydrogen phosphate, 10-methacryloyloxydecyl dihydrogen phosphate (MDP), bis-(10,10'-methacryloyloxydecyl)hydrogen phosphate, glycerol phosphate dimethacrylate, hydroxyethyl methacryloyl dihydrogen sulfate, hydroxypropyl methacryloyl dihydrogen sulfate, 10-methacryloyloxydecyl dihydrogen sulfate, hydroxyethyl methacryloyl hydrogen sulfite, hydroxypropyl methacryloyl hydrogen sulfite, 10-methacryloyloxydecyl hydrogen sulfite, 4-Methacryloyloxyethyl trimellitic acid, 4-methacryloyloxyethyl trimellitic anhydride.Preference is given to the use of hydroxyethyl methacryloyl dihydrogen phosphate, hydroxypropyl methacryloyl dihydrogen phosphate, 10-methacryoyloxydecyl dihydrogen phosphate (MDP), glycerol phosphate dimethacrylate, 4-methacryloyloxyethyl trimellitic acid, 4-methacryloyloxytrimellitic anhydride, and their respective anhydrides, which can be converted into the corresponding functional groups containing acidic protons by subsequent hydrolysis.

[0138] Particularly preferred is the use of polymerizable monomers with phosphate groups containing acidic protons and especially of MDP (CAS No. 85590-00-7) as the only or as one of several monomers with a functional group.

[0139] (ii) Also preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims) comprising 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other:

[0140] R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0141] R 2 and R 3 are the same or different and are each selected from the group consisting of H and structures of formula (II) (II), with

[0142] X is H or CH3 and

[0143] 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

[0144] atom is 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, and as one or more further components additionally comprising 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 particles and / or ytterbium trifluoride particles, wherein the composition is suitable for use as a dental adhesive or for use as a component of a dental multi-component adhesive.

[0145] The preferred composition possesses particularly good shear bond strength due to the presence of component (f). Tables 3 and 4 show that higher shear bond strengths are achieved with higher filler particle concentrations—the concentration of silicon dioxide particles is varied in Table 3, and the concentration of ytterbium trifluoride particles is varied in Table 4. The decrease in shear bond strength at very high filler particle concentrations is attributable to the simultaneous decrease in the BisGMA concentration in the example compositions (for the influence of Bis-GMA, see the above comments on i).

[0146] Particularly preferably, the preferred composition comprises silicon dioxide particles and ytterbium trifluoride particles as filler particles when achieving high shear strength is paramount. Example 18 shows that particularly high shear bond strength can be achieved by using these two filler particles simultaneously. This synergistic effect is surprising.

[0147] Particularly preferably, such a preferred composition according to the invention also comprises components b) and / or c) (preferably b and c) as described above under (i). The statements regarding preferred embodiments apply accordingly. (iii) Also preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims) comprising 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other: R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0148] R 2 and R 3are the same or different and are each selected from the group consisting of H and structures of formula (II) (II), with

[0149] X is H or CH3 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 and

[0150] 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, in an amount of up to 10% by weight, preferably up to 8% by weight, based on the total mass of the composition, the composition being suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive.

[0151] A preferred composition comprises a maximum of 10% by weight of film formers (component a), since at concentrations above 10% by weight the shear bond strength is reduced, at least in some cases.

[0152] Example 6 from Table 2 shows that the shear bond strength decreases with an increase in the film former concentration from 5 wt.% to 10 wt.%. When increasing from 10 wt.% to 12 wt.%, the shear bond strength decreases more significantly, with a change from 25.26 MPa to 19.11 MPa. The storage stability decreases when changing from 5 wt.% to 10 wt.% film former from "+++" to Both storage stabilities can still be considered good, but there is a trend toward decreasing storage stability with increasing film-forming agent concentration. It is therefore preferred that the concentration of film-forming agents be up to 10 percent by weight, based on the total mass of the composition.

[0153] Particularly preferably, such a preferred composition according to the invention also comprises components b) and / or c) (preferably b and c) as described above under (i) and / or component f) as described above under (ii). Particularly preferably, all components b, c, and f are present simultaneously. The statements regarding preferred embodiments apply accordingly.

[0154] (iv) Also preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims), 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other:

[0155] R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0156] R 2 and R 3 are the same or different and each selected from the

[0157] Group consisting of H and structures of formula (II) (II), with

[0158] X is H or CH3 and

[0159] 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 and

[0160] R 4 and R 5 are the same or different and each represent a single bond or an alkylene group with a total of 1 to 4 carbon atoms, where R 2 and / or R 3 in individual, a plurality of or all structural units of the repeating units of formula (I) are structures of formula (II) and wherein the composition is suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive.

[0161] Particularly preferably, in individual, a plurality of or all structural units of the formula (I) R 2 a structure of formula (II) and R 3 is H or

[0162] R 3 a structure of formula (II) and R 2 is H.

[0163] This means that in the repeating units of a preferred composition according to the invention according to the above formula (I) R 2 or R 3 preferably not exclusively and everywhere H.

[0164] The preferential functionalization of the film formers with radically polymerizable structures of formula (II) enables a covalent linking of the film formers with further radically polymerizable components, preferably with radically polymerizable acidic monomers (component b) and / or the radically polymerizable monomers (component c), particularly preferably with radically polymerizable monomers of components b and c, during a radical polymerization. The film former then becomes part of the (cross-)linked polymer through radical polymerization. By preferably also present carboxylate functions in the film formers (in R 2 and / or R 3 ) also ensures an ionic interaction with the tooth substance.

[0165] Film formers whose repeating units are exclusively structural units in which both R 2 as well as R 3Both are H, are only capable of coordination to the tooth structure and do not form significant interactions with radically polymerizable components of the composition. This results in a comparatively weaker polymer network and fewer available binding sites remain on the tooth structure, especially for the (preferably radically polymerizable) acidic monomers. This is often perceived as a disadvantage, but is certainly desirable for specific applications.

[0166] Such a preferred composition according to the invention particularly preferably also comprises components b) and / or c) (preferably b and c) as described above under (i) and / or component f) as described above under (ii). Particularly preferably, all components b, c and f are present simultaneously. Also particularly preferred is such a preferred composition according to the invention in which, as described under (iii), film formers (component a as defined above and in the claims) are present in a total amount of up to 10 percent by weight, based on the total mass of the composition. The above statements regarding preferred embodiments apply accordingly.

[0167] (v) Also preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims), 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other:

[0168] R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0169] R 2 and R 3 are the same or different and are each selected from the group consisting of H and structures of formula (II) (II), with

[0170] X is H or CH3 and

[0171] 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 and

[0172] R 4 and R 5are the same or different and each represent a single bond or an alkylene group having a total of 1 to 4 carbon atoms, wherein the composition comprises, as polymers whose repeating units are or comprise structural units according to formula (I), not only polymers selected from the group consisting of poly(methyl vinyl ether-maleic acid), poly(butyl vinyl ether-maleic acid), poly(styrene-maleic acid) and salts thereof, wherein the composition preferably comprises less than 10% by weight, more preferably less than 5% by weight, particularly preferably less than 1% by weight of polymers selected from the group consisting of poly(methyl vinyl ether-maleic acid), poly(butyl vinyl ether-maleic acid), poly(styrene-maleic acid) and salts thereof, based on the total amount of the film formers, and / or less than 1% by weight, preferably less than 0.5% by weight, particularly preferably less than 0.1% by weight.-% of polymers selected from the group consisting of poly(methyl vinyl ether maleic acid), poly(butyl vinyl ether maleic acid), poly(styrene maleic acid) and salts thereof, based on the total amount of the composition, particularly preferably does not comprise any polymers selected from the group consisting of poly(methyl vinyl ether maleic acid), poly(butyl vinyl ether maleic acid), poly(styrene maleic acid) and salts thereof, and / or wherein the composition preferably does not comprise, as polymers whose repeating units are or comprise structural units according to formula (I), only polymers selected from the group consisting of polymers whose repeating units are structural units according to formula (I), wherein in these structural units according to formula (I) R. 2 and R 3are each H, and their salts, the composition being suitable for use as a dental adhesive or for use as a component of a multi-component dental adhesive.

[0173] The polymer poly(methyl vinyl ether-maleic acid) is often abbreviated as PMVE-MA. The polymer poly(butyl vinyl ether-maleic acid) is often abbreviated as PBVE-MA. The polymer poly(styrene-maleic acid) is often abbreviated as PS-MA.

[0174] The repeating units of these polymers are given below:

[0175] Formula (X) shows the repeating unit of poly(methyl vinyl ether-maleic acid), formula (XI) shows the repeating unit of poly(butyl vinyl ether-maleic acid), and formula (XII) shows the repeating unit of poly(styrene-maleic acid).

[0176] These are therefore polymers whose repeating units are structural units according to formula (I), where in the structural units according to formula (I) R 2 and R 3 are each H. Such polymers and their salts (as they are formed in particular by releasing protons from groups R 2 or R 3 can be formed) are generally not particularly preferred in the context of the present invention.

[0177] Compositions with higher concentrations of poly(methyl vinyl ether-maleic acid), poly(butyl vinyl ether-maleic acid), poly(styrene-maleic acid) and other polymers whose repeating units are structural units according to formula (I), wherein in these structural units according to formula (I) R 2 and R 3 are each H, show - in comparison with compositions with higher concentrations of film formers, where R 2 and / or R 3 (preferably R 2 or R3 ) have a structure of formula (II) - exhibit weaker cross-linking and bonding to the tooth substance. This is undesirable in many cases. Reference is made to the above comments.

[0178] Such a preferred composition according to the invention particularly preferably also comprises components b) and / or c) (preferably b and c) as described above under (i) and / or component f) as described above under (ii). Particularly preferably, all components b, c and f are present simultaneously. Also particularly preferred is such a preferred composition according to the invention in which, as described under (iii), film formers (component a as defined above and in the claims) are present in a total amount of up to 10 percent by weight, based on the total mass of the composition. The above statements regarding preferred embodiments apply accordingly.

[0179] (vi) Preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims) 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other:

[0180] 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 each selected from the

[0181] Group consisting of H and structures of formula (II) (II), with

[0182] X is H or CH3 and

[0183] 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 and

[0184] R 4 and R 5 are the same or different and each represent a single bond or an alkylene group with a total of 1 to 4 carbon atoms, the composition being producible by the manufacturing process defined in the claims, ie in particular by a process comprising the following steps:

[0185] Providing or preparing a copolymer of the general formula (V)

[0186] Reacting the copolymer of general formula (V) with a compound of general formula (VI), so that one or more film formers result as defined in claim 1 wherein R 1 , R 4 , R 5, X and L each independently have the meaning given in claim 1, wherein the composition is suitable for use as a dental adhesive or for use as a component of a dental multicomponent adhesive. The above-mentioned steps are the steps of the manufacturing process according to the invention; preferred embodiments of this manufacturing process also apply to the preferred composition.

[0187] The above-mentioned manufacturing process produces film formers in which R 2 and / or R 3 , preferably R 2 or R 3 a structure of formula (II). As already explained above, compositions containing film formers in which at least one of the radicals R 2 or R 3a structure of formula (II), better (cross-)linking of the polymer and better adhesion of the radically polymerizable acidic monomer (component b) to the tooth substance are achieved. - M -

[0188] Particularly preferably, such a preferred composition according to the invention also comprises components b) and / or c) (preferably b and c) as described above under (i) and / or component f) as described above under (ii). Particularly preferably, all components b, c, and f are present simultaneously. Also particularly preferred is such a preferred composition according to the invention in which, as described under (iii), film formers (component a as defined above and in the claims) are present in a total amount of up to 10 percent by weight, based on the total mass of the composition. The above statements regarding preferred embodiments apply accordingly. The provisions according to the statements under (iv) and (v) are also preferred for the preferred compositions according to the invention that can be produced by the production process according to the invention.

[0189] (vii) Also preferred is a composition according to the invention (preferably a composition according to the invention as referred to above or below as preferred or defined in the dependent claims), 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other:

[0190] 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 each selected from the

[0191] Group consisting of H and structures of formula (II) (II), with

[0192] X is H or CH3 and

[0193] 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

[0194] atom a polyethylene glycol group or a polypropylene glycol group and

[0195] R 4 and R 5are identical or different and each represents 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 dental multi-component adhesive, each suitable for producing a permanent bond between tooth substance and a filling, ceramic veneer, or all-ceramic restoration. The compositions according to the invention described above under (i), (ii), (iii), (iv), and (vi) are each particularly suitable for producing a permanent bond between tooth substance and a filling, ceramic veneer, or all-ceramic restoration.

[0196] As already explained above, compositions according to the invention are particularly well suited for establishing a permanent bond between the tooth substance and the filling, ceramic veneer, or all-ceramic restoration due to their high shear bond strength. For dental restorations, a permanent and firm bond between the tooth and the filling material or denture is generally desired, which must, above all, withstand the mechanical stresses that regularly occur (e.g., due to chewing). In practice, therefore, compositions for use as dental adhesives or dental adhesive compositions are sought that possess the highest possible shear bond strength.

[0197] Aspects of the present invention, including preferred embodiments, are set out below in a structured form:

[0198] 1 . 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other: R 1 means an alkoxy group with a total of 1 to 10 carbon atoms or a phenyl group,

[0199] R 2 and R 3 are the same or different and are each selected from the group consisting of H and structures of formula (II) (II), with

[0200] X is H or CH3 and

[0201] 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

[0202] atom a polyethylene glycol group or a polypropylene glycol group and

[0203] R 4 and R 5are identical or different and each represent a single bond or an alkylene group having a total of 1 to 4 carbon atoms, wherein the composition is suitable for use as a dental adhesive or for use as a component of a dental multi-component adhesive. Composition according to aspect 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 aspect 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 aspect 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) for silicon dioxide particles is in the range from 10 to 15 nm and / or for ytterbium trifluoride particles is in the range from 7 to 60 nm, preferably in the range from 7 to 50 nm, particularly preferably in the range from 20 to 40 nm. Composition according to one of aspects 2 to 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 of 1 : 20 to 10 : 1, preferably in the range of 1 : 3 to 1 : 1. Composition according to one of the preceding aspects,preferably according to one of aspects 2 to 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 component b) in an amount in the range from 1 to 5 percent by weight, and / or component c) in an amount in the range from 45 to 79 percent by weight, and / or 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 component e) in an amount in the range from 0.01 to 0.5 percent by weight, and / or component f) in an amount in the range from 1 to 20 percent by weight, and / or 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% by weight, particularly preferably in the range of 15 to 25% 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 any one of aspects 1 to 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 aspect 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,

[0204] - a second component comprising constituents g) and i), wherein the first and second components are each present as separate individual components. Composition according to aspect 8, wherein constituent g) is present 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 constituent 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 toluenesulfinate and tetracoordinate borates, and / or constituent i) is present 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 as an additional component]) comprises one or more solubilizers, preferably 2-butanone, wherein component j) is preferably present 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. Composition according to one of aspects 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 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 aspects, preferably according to one of aspects 2 to 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 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 aspects 2 to 11, wherein the filler particles of component f) are silicon dioxide particles and component f) is present 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 present in the composition in an amount ranging from 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 percent by weight of ytterbium trifluoride particles, each based on the total mass of the composition. Composition according to one of the preceding aspects, wherein:

[0205] R 1 means a methoxy group or phenyl group, preferably a methoxy group and / or

[0206] L is an alkylene group having 2 or 3 carbon atoms, preferably having 2 carbon atoms and / or

[0207] R 4 and R 5are each a single bond, where preferably:

[0208] R 1 is a methoxy group and R 4 and R 5 are each a single bond and L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

[0209] 14. Composition according to any one of the preceding aspects, 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.

[0210] 15. A process for preparing a composition according to any one of aspects 1 to 6 or 11 to 14, comprising the following steps:

[0211] 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);

[0212] II) Mixing the components prepared or provided in step I) to form the composition. A process for producing a multicomponent composition according to any one of aspects 7 to 14, comprising the following steps:

[0213] 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);

[0214] II) distribution of the components produced or provided in step I) among several components, wherein preferably components b) and c) are distributed among components other than component i);

[0215] III) separate mixing of the components distributed in step II) among the multiple components, so that the multi-component composition results, wherein preferably the one or more film formers a) and the components b), c), d), e) and f) are distributed among a first of two components and the components g) and i), optionally additionally together with the component j), are distributed among a second of two components, so that a two-component composition results. Composition according to one of aspects 1 to 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 which is carried out on the human or animal body, preferably for specific use in a therapeutic method for

[0216] - direct or indirect restoration of teeth, and / or

[0217] - intraoral repair of fillings, ceramic veneers and / or all-ceramic restorations, and / or

[0218] - Treatment of hypersensitive tooth necks, and / or

[0219] - Sealing of dental cavities before amalgam restorations and / or before temporary cementation, or in a therapeutic procedure as

[0220] - dental universal adhesive and / or

[0221] - Protective varnish for glass ionomer cement fillings. Composition according to any one of aspects 7 to 14 for use in a therapeutic method for securing root posts. Method for the therapeutic treatment of teeth comprising the following steps:

[0222] 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,

[0223] II) producing or providing a composition according to any one of aspects 1 to 14,

[0224] III) Applying the composition prepared or provided in step II) to the tooth area to be treated prepared in step I). Method for producing a composition according to one of aspects 1 to

[0225] 14, with the following steps:

[0226] 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 defined in any one of aspects 1 to 14 where R 1 , R 4 , R 5 , X and L each independently have the meaning given in any of aspects 1 to 14.

[0227] The invention is explained in more detail below using examples. The following examples are intended to describe and explain the invention in more detail without limiting its scope.

[0228] Synthesis Examples 1 to 13 each relate to the preparation of a composition according to the invention, namely a film former 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.

[0229] 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)

[0230] In a 1-liter round-bottom 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 N2 and then kept under a N2 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.

[0231] 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 (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. This gave 121.84 g (86% of the theoretical yield) of a film former a) for compositions according to the invention in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

[0232] In a 1 liter round-bottomed flask, hydroxyethyl methacrylate (HEMA; 0.32 mol;

[0233] 41.68 g) in 200 mL of THF at room temperature. The solution was degassed for 30 min under a stream of N2 and then kept under a N2 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.

[0234] 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 was taken up in dichloromethane (400 ml) and washed with 0.1 M HCl (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 117.6 g (83% 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.

[0235] In a 1-liter round-bottom flask, hydroxypropyl methacrylate (HPMA; 0.32 mol; 46.14 g; mixture of isomers, see below) was dissolved in 200 mL of THF at room temperature. The solution was degassed for 30 min under a stream of N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The resulting residue was taken up in dichloromethane (400 ml) and washed with 0.1 M HCl (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered, and the solvent was then removed. 118.37 g (81% of dry matter) of the product were obtained.) g of a film former a) for compositions according to the invention was 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.

[0236] 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).

[0237] In a 1-liter round-bottom flask, hydroxypropyl methacrylate (HPMA; 0.32 mol; 46.14 g, mixture of isomers, 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 N2 and then kept under a N2 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.

[0238] 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 was taken up in dichloromethane (400 ml) and washed with 0.1 M HCl (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 112.82 (77% of dry matter) 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.

[0239] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was taken up in dichloromethane (400 mL) and washed with 0.1 M HCl (3 x 400 mL). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 142.75 g (80% of dry matter) of the product were obtained.) of a film former a) for compositions according to the invention 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:.

[0240] In a 1-liter round-bottom 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 N2 and then kept under a N2 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.

[0241] 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 was taken up in dichloromethane (400 ml) and washed with 0.1 M HCl (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 128.54 g (72% 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.

[0242] Synthesis example 7:

[0243] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was taken up in dichloromethane (400 mL) and washed with 0.1 M HCl (3 x 400 mL). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 130.27 g (77% of dry matter) were obtained.) of a film former a) for compositions according to the invention in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

[0244] In a 1-liter round-bottom 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 N2 and then kept under a N2 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.

[0245] 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 was taken up in dichloromethane (400 ml) and washed with 0.1 M HCl (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 126.36 g (74% 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.

[0246] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was taken up in dichloromethane (400 mL) and washed with 0.1 M HCl (3 x 400 mL). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 106.17 g (79% of dry matter) were obtained.) of a film former a) for compositions according to the invention in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands. 10:

[0247] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was taken up in dichloromethane (400 mL) and washed with 0.1 M HCl (3 x 400 mL). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 112.30 g (85% of dry matter) were obtained.) of a film former a) for compositions according to the invention in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands.

[0248] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The resulting residue was dissolved in dichloromethane (400 ml) and washed with 0.1 M HCl (3 x 400 ml). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered, and the solvent was subsequently removed.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. 12:

[0249] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was taken up in dichloromethane (400 mL) and washed with 0.1 M HCl (3 x 400 mL). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 105.57 g (66% of dry matter) were obtained.) of a film former a) for compositions according to the invention in the form of a colorless, amorphous powder. The successful reaction was confirmed by IR spectroscopy by the loss of the characteristic anhydride bands. 13:

[0250] In a 1-liter round-bottom 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 N2 and then kept under a N2 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 at 40 °C for 24 h and then cooled to room temperature. The solvent was removed under reduced pressure. The residue was taken up in dichloromethane (400 mL) and washed with 0.1 M HCl (3 x 400 mL). The organic phase was separated from the aqueous phase using a separatory funnel and dried over anhydrous magnesium sulfate. The solution was filtered and then freed from the solvent. 106.96 g (69% of dry matter) were obtained.) of a film former a) for compositions according to the invention 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 the compositions according to the invention and further investigations.

[0251] 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 tested for their shear bond strength and storage stability, compared with a non-inventive composition. The tests conducted show the person skilled in the art how to achieve compositions with specific product properties by simply varying the components and their proportions.

[0252] In detail:

[0253] C) Preparation of test compositions based on synthesis examples 1 to 13:

[0254] Monomers, film formers, initiators, co-initiators, inhibitors, and solvents were weighed in the specified proportions according to 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) and a non-inventive comparative composition (Example 1). The compositions used in the examples are also referred to below as test compositions or adhesives.

[0255] The compositions used in the examples are single-component; however, analogous results were also obtained with multi-component compositions.

[0256] D) Testing the shear bond strength

[0257] The resulting test compositions were each subjected to a shear test. The shear bond strength tests were conducted in accordance with ISO 29022:2013 - Dentistry - Adhesion - Recessed blade shear bond strength test, unless otherwise specified.

[0258] Details can be found in the following text:

[0259] 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.

[0260] The tooth surface was standardized by coarse 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 prepared tooth surface was cleaned of impurities under running deionized water and then freed of excess water with a short burst of air or lightly dabbing with a paper towel. The teeth were not overdried, thus preventing morphological changes in the tooth structure.

[0261] 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 (the adhesive) were removed by blasting with oil- and water-free compressed air for 5 seconds, followed by light curing for 10 seconds (Celalux 2, 420-490 nm, 1000 W / cm 2 ).

[0262] After the adhesive layer had cured, the embedded tooth specimen was inserted into a composite screw clamp including a mold (from ISO 29022:2013 - Ultradent Products, South Jordan).

[0263] The filling cavity of the insert mold was placed on the surface of the tooth and checked for adequate fit. The appliance was then secured with screws.

[0264] Inserting 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 tamper (composite tamper), and a tight contact was achieved 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). While avoiding loads that could have a negative effect on the adhesive bond (tensile, torsion, shear, etc.), the composite specimen fitted 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 design with recessed blade) was installed in a universal testing machine (Zwick, Roell). The composite specimen, locked in its holder, was placed in the holder under the crosshead with the recessed blade, aligned centrally on the composite cylinder and against the tooth, and positioned so that the recess in the crosshead and the composite cylinder to be sheared off slid into each other without generating stresses.

[0265] E) Storage stability

[0266] 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.

[0267] “+++” Gelation or polymerization only after more than 3 months

[0268] “++” Gelation or polymerization after 1 to 3 months

[0269] “+” Gelation or polymerization after 7 days to 1 month

[0270] “0” gelation or polymerization in less than 7 days

[0271] For use as dental adhesives, compositions that do not gel or polymerize at all or only after several months under accelerated aging conditions are preferred. For the purposes of this task, test compositions with a rating of "+++" are preferred, while those with a rating of "0" are least preferred.

[0272] F) Results

[0273] The components of the tested compositions as well as the shear bond strength values ​​and storage stability 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

[0274] Function Abbreviation CAS No. Substance

[0275] Acidic Mo10 methacryloyloxydecyl phosphate

[0276] MDP 85590-00-7 nomer

[0277] Monomer 2,2-Bis[4-methacryloyloxypolyethoxy-

[0278] BisGMA 1565-94- 2 phenyl]propan

[0279] Monomer TEGDMA 109-16-0 Triethylenglycoldimethacrylat

[0280] Monomer HEMA 868-77-9 2-Hydroxyethylmethacrylat

[0281] Initiator CQ 10373-78-1 DL-Campherchinon

[0282] Co-Initiator EDB 10287-53-3 4-(Dimethylamino)benzoesäureethylester

[0283] Inhibitor BHT 128-37-0 2,6-Di-tert.-butyl-4-methylphenol

[0284] Tabelle 2

[0285] In the example compositions according to Table 2 (Examples 2 to 6), the proportions of the film former (prepared according to 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 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, i.e. from a proportion of 10.00 wt.% of the film former from inventive synthesis example 1.

[0286] Table 3

[0287] In the examples shown in Table 3, the proportions of the monomer BisGMA and the filler silicon dioxide (SiC>2) were varied. In Examples 11 and 12 of Table 3, a decrease in storage stability is observed, which is presumably due to the higher proportion of 8.00 wt.% SiO2 in Example 11 and 10.00 wt.% SiO2 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.% SiO2.

[0288] Table 4

[0289] In the example compositions according to Table 4, the proportions of the monomer BisGMA and the filler ytterbium trifluoride (YbF3) were varied. Example 17 has the highest proportion of YbF3 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 presumably due to the occurrence of a synergistic effect when silicon dioxide particles (SiC>2) and ytterbium trifluoride particles (YbFa) are used simultaneously as filler particles.

[0290] Table 5 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, 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) was used, showed not only high shear bond strength but also very good storage stability. Example compositions 21 and 22 with film formers according to 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.

[0291] Table 6

[0292] In the example compositions shown in Table 6, the type of film former was varied according to the inventive synthesis examples 8 to 13. Examples 25 and 27 show that film formers prepared with poly(ethyl vinyl ether-alt-maleic anhydride) (used in Synthesis Example 9) and film formers prepared with poly(styrene-alt-maleic anhydride) (used in Synthesis Example 10) also exhibit 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.

Claims

Patent claims: 1 . 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 for R 1 , R 2 , R 3 , R 4 and R 5 in each structural unit independently of each other: R 1 means an alkoxy group with 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 formula (II) (II), with X is H or CH3 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 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.

2. 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.

3. 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.

4. Composition according to one of the preceding claims, additionally comprising as one or more further components: 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 particles and / or ytterbium trifluoride particles.

5. Composition according to claim 4, 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.

6. Composition according to one of the preceding claims, additionally comprising as one or more further components: d) one or more photoinitiators, and / or e) one or more inhibitors, 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.

7. Composition according to one of claims 2 to 6, wherein the composition comprises a component c) as defined in claim 2 or 3 and 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 composition comprises a component c) as defined in claim 2 or 3 and a component f) as defined in claim 4 or 5 and wherein 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 composition contains a component f) as defined in claim 4 or 5 and wherein 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.

8. Composition according to one of the preceding claims, comprising the one or more film formers a) in an amount of up to 10% by weight, preferably in an amount in the range from 1 to 10% by weight, particularly preferably in an amount in the range from 2 to 8% by weight, and / or component b) as defined in claim 2 in an amount in the range from 1 to 5% by weight, and / or component c) as defined in claim 2 or 3 in an amount in the range from 45 to 79% by weight, and / or component d) as defined in claim 6 in an amount in the range from 0.1 to 3.5% by weight, preferably in the range from 0.1 to 1.5% by weight, and / or component e) as defined in claim 6 in an amount in the range from 0.01 to 0.5% by weight, and / or component f) as defined in claim 4 or 5 in an amount in the range from 1 to 20 Percent by weight, and / or the component g) as defined in claim 6 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 from 15 to 25 percent by weight, very particularly preferably in the range from 17.5 to 20 percent by weight, and / or the component h) as defined in claim 6 in an amount in the range from 0.1 to 2 percent by weight, in each case based on the total mass of the composition.

9. Composition according to any one of the preceding claims, wherein R 2 and / or R 3 in individual, a plurality of or all structural units of the repeating units of formula (I) are structures of formula (II).

10. Composition according to one of the preceding claims, wherein the composition is multi-component, wherein the composition preferably Component b) as defined in claim 2, Component c) as defined in claims 2 or 3, Component d) as defined in claim 6, and Component g) as defined in claim 6, and as 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).

11. Composition according to claim 10, 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) as defined in the preceding claims, and - a second component comprising the components g) and i) as defined in the preceding claims, wherein the first and the second component are each present as separate individual components.

12. Composition according to claim 11, wherein 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-coordinate borates, and / or 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 as an additional component]) comprises 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.

13. Composition according to one of claims 11 or 12, wherein the first component comprises one or more film formers a) in an amount in the range of 1 to 10% by weight, and / or component b) in an amount in the range of 1 to 5% by weight, and / or component c) in an amount in the range of 45 to 96% by weight, and / or component d) in an amount in the range of 0.1 to 1.5% by weight, and / or component e) in an amount in the range of 0.01 to 0.5% by weight, and / or component f) in an amount in the range of 1 to 20% by weight, each based on the total mass of the first component.

14. Composition according to one of the preceding claims, preferably according to one of claims 2 to 13, comprising the one or more film formers a) in an amount in the range from 5 to 8 percent by weight, preferably in the range from 6 to 8 percent by weight, and / or the component f) as defined in claim 4 or 5 in an amount in the range from 2 to 15 percent by weight, preferably in the range from 5 to 12 percent by weight, particularly preferably in the range from 6 to 8 percent by weight, in each case based on the total mass of the composition.

15. A composition according to any one of claims 2 to 14, comprising filler particles of component f) as defined in claim 4 or 5, wherein the filler particles of component f) are silicon dioxide particles and component f) is present in the composition in an amount in the range of 2 to 8 weight percent, preferably in the range of 5 to 6 weight percent, based on the total mass of the composition, or the filler particles of component f) are ytterbium trifluoride particles and component f) is present in the composition in an amount in the range of 12 to 15 weight percent, based on the total mass of the composition, or component f) consists of 2 to 4 weight percent of silicon dioxide particles and 2 to 4 weight percent of ytterbium trifluoride particles, preferably of 3 weight percent of silicon dioxide particles and 3 weight percent of ytterbium trifluoride particles,each based on the total mass of the composition., 16. Composition according to any one of the preceding claims, wherein: R 1 means 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, where preferably: R 1 is a methoxy group and R 4 and R 5 are each a single bond and L is an alkylene group with 2 or 3 carbon atoms, preferably with 2 carbon atoms.

17. A composition according to any 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.

18. A process for preparing a composition according to any one of claims 1 to 9 or 14 to 17, 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 prepared or provided in step I) to produce the composition.

19. A process for preparing a multi-component composition according to any one of claims 10 to 17, 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); II) distribution of the components produced or provided in step I) among several components, wherein preferably components b) and c) are distributed among components other than component i); III) separate mixing of the components distributed in step II) among the several components, so that the multi-component composition results, wherein preferably the one or more film formers a) and the components b), c), d), e) and f) are distributed among a first of two components and the components g) and i), optionally additionally together with the component j), are distributed among a second of two components, so that a two-component composition results.

20. Composition according to one of claims 1 to 17 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, 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 cementation, or in a therapeutic procedure as - dental universal adhesive and / or - Protective varnish for glass ionomer cement fillings.

21. A composition according to any one of claims 10 to 17 for use in a therapeutic method for securing root posts.

22. 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 any one of claims 1 to 17, III) Applying the composition prepared or provided in step II) to the tooth area to be treated prepared in step I).

23. A method for producing a composition according to any one of claims 1 to 17, 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 result as defined in any one of claims 1 to 14, wherein R 1 , R 4 , R 5 , X and L each independently of one another in one of the Proverbs 1 to 14 have the meaning given.

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