HK1261688A1 - Dental composition - Google Patents

Description

Dental composition

Technical Field

The present invention relates to a polymerizable dental composition comprising a specific polymerizable compound. Furthermore, the present invention relates to the use of specific polymerizable compounds for the preparation of dental compositions. The polymerizable compounds of the present invention are multifunctional polymerizable monomers which are copolymerizable with conventional (meth) acrylates, (meth) acrylamides and allyl ethers, and which provide dental compositions having low viscosity and excellent biocompatibility.

Background

Polymerizable dental compositions containing polymerizable compounds are known. Conventionally, polymerizable dental compositions are provided for a wide range of applications and, therefore, different requirements have to be met. For example, the polymerizable dental composition can be a dental adhesive composition, a bonding agent, a pit and fissure sealant, a dental desensitizing composition, a pulp capping composition, a dental composite, a dental glass ionomer cement, a dental cement, a root canal sealer composition, or a dental impregnant.

In general, (meth) acrylates are attributed to their excellent propertiesFree radical polymerization reactivity for use as polymerizable component in polymerizable dental compositions, the excellent free radical polymerization reactivity may be based on at Δ_RH ═ 80 to-120 kJ/mol. To provide crosslinking capability, multifunctional (meth) acrylates such as bis-GMA were used in dental applications as early as 1962.

EP 2895138A 1 discloses polymerizable dental compositions comprising N-substituted acrylic amide compounds having a divalent C optionally containing a carbon-carbon double bond₁To C₂₀A linking group in the form of an alkylene group, however the position of the carbon-carbon double bond within the alkylene group is generally not defined. EP 2895138A 1 discloses only one example of such polymerizable compounds, namely N, N' -diallylamino- (2E) -but-2-ene (BAABE). In addition, the polymerizable compounds of EP 2895138 a1 comprise an allyl group bonded to the nitrogen atom of the polymerizable (meth) acrylamide group, which allyl group is taught to provide for an advantageous ring polymerization reaction.

European patent applications with application numbers EP 15178515 and EP 15188969 represent prior art according to clause 54(3) EPC and disclose polymerizable dental compositions that may comprise a polymerizable compound, wherein two N-substituted acrylic amide moieties are linked via a linking group. The linking group may represent C₂To C₁₂Or C₁₈Alkenylene, wherein the position of the carbon-carbon double bond in the alkenylene linking group is generally undefined. As specific examples of polymerizable compounds having such alkenylene linking groups, EP 15178515 and EP 15188969 disclose N, N' -diallyl-1, 4-bisacrylamido- (2E) -but-2-ene (BAABE).

Disclosure of Invention

The problem of the present invention is to provide polymerizable dental compositions comprising specific polymerizable compounds which are copolymerizable with conventional (meth) acrylates, (meth) acrylamides and allyl ethers and which have a favourable enthalpy of polymerization, a low viscosity and an excellent biocompatibility.

The present invention provides a polymerizable dental composition comprising

(a) Polymerizable compounds of the following formula (I):

X'-L-X"

(I)

wherein

X' represents a group of the following formula (II) or (III):

wherein

Dotted line represents

A double or triple bond, wherein in the presence of a triple bond, R is absent⁴And R⁵；

The jagged lines indicate that formulas (II) and (III) encompass any of the (E) or (Z) isomers,

z' and Z ", which may be the same or different, independently represent an oxygen atom, a sulfur atom or > N-R, wherein

R is a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group, or a group of formula (IV):

wherein

The jagged lines indicate that formula (IV) includes any of the (E) or (Z) isomers,

R¹¹and R¹²，

May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group;

R¹³and R¹⁴，

May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group; or R¹³And R¹⁴Together represent an oxygen atom which together with the adjacent carbon atoms forms a carbonyl group;

R¹and R²，

May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted with at least one moiety selected from the group consisting of hydroxyl, alkoxy or acidic groups;

R³represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group;

R⁴and R⁵，

May be the same or different, independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted with an alkoxy or acidic group;

R⁶represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which groups can be substituted by alkoxy groups;

x "represents a moiety selected from the group consisting of a hydroxyl group, a thiol group, an alkoxy group and an acidic group, or a moiety of the following formula (V) or (VI):

wherein

The jagged lines indicate that formula (V) encompasses any of the (E) or (Z) isomers,

z and Z, which may be the same or different, independently represent an oxygen atom, a sulfur atom or > N-R', wherein

R' is a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted with an alkoxy or acidic group; or R' is independently a group of formula (IV) as defined for R;

R⁷and R⁸

May be the same or different, independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, said group being capable of being substituted with at least one moiety selected from the group consisting of a hydroxyl group, a thiol group, an alkoxy group and an acidic group;

R⁹represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group;

R¹⁰represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which groups can be substituted by alkoxy groups;

or alternatively, the one or more of,

R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰r' and, if present, R¹¹、R¹²、R¹³And R¹⁴Any two residues in (a) can together represent an alkylene or alkenylene group, which can be substituted by an alkoxy group, an acidic group or-NR^▲R^▼Is substituted by radicals in which R^▲And R^▼Independently of one another, represents a hydrogen atom or an alkyl group; or

R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰R' and, if present, R¹¹、R¹²、R¹³And R¹⁴Any two residues in (A) which are not geminal or vicinal groups can together represent a single bond,

wherein the single bond or the optionally substituted alkylene or alkenylene together with the bridging atom to which the residue is attached form a 3-to 8-membered saturated or unsaturated ring,

wherein the polymerizable compound of formula (I) can include one or more of the 3-to 8-membered saturated or unsaturated rings; and is

L may be present or absent, represents a divalent linking group when present, and X' and X "are directly bonded by a single bond when absent.

(b) A photosensitizer, and

(c) and (4) an iodine salt.

The invention also provides the use of a polymerizable compound of formula (I) for the preparation of a dental composition.

The invention is based on the recognition that the polymerizable compounds of formula (I) have a polymerization enthalpy which is comparable to or better than the polymerization enthalpy of conventional (meth) acrylates, (meth) acrylamides and allyl ethers. Furthermore, the invention is based on the recognition that the viscosity of the compounds of formula (I) is within the range of (meth) acrylates commonly used in the field of dental compositions. In addition, the polymerizable compounds of formula (I) provide an advantageous maximum polymerization rate and desirable mechanical properties, such as flexural strength (flexalstrength).

Drawings

FIG. 1 shows the parametric Refractive Indices (RI) (n) of the compounds of formula (I) according to the invention and of the comparative compounds (C1), (C2) and (C3) measured at 20 ℃ represented as (Ib) and (Ic)_D ²⁰) And a viscosity η measured at 23 ℃ (η)_23℃) Bar graph of (2). The compound (Ib) is N, N '-bisacryloyl-N, N' -bisallyl-2, 4-pent-2-enediamine and is reactedCompound (Ic) was N, N '-bisacryloyl-N, N' -bisaropyl-1, 4-but-2-enediamine comparative compound (C1) was N, N '-diacetyl-N, N' -bisallyl-1, 4-but-2-enediamine, (C2) was N, N '-bisacryloyl-N, N' -bisallyl-1, 4-butanediamine and C (3) was N, N '-bisacryloyl-N, N' -bisallyl-1, 4-butanediamine RI in fig. 1 is depicted by dark gray bars and viscosity η is depicted by light gray shaded bars for comparative compound (C1) viscosity η was not determined (indicated by "×").

FIG. 2 shows a bar graph of the enthalpy of polymerization (Δ H), and FIG. 3 shows the maximum heat flow time, i.e.the time taken to reach the highest polymerization rate (t)_max) Bar graph of (2). Determination of Δ H and t for compositions containing Compounds of formula (Ib), (Ic) or comparison Compounds (C1), (C2) or (C3), respectively_max0.22 to 0.35 mol% of a stabilizer, 0.3 wt% of Camphorquinone (CQ) was determined as a sensitizer, and 0.4 wt% of ethyl 4- (dimethylamino) benzoate (DMABE) was determined as a co-initiator. For compound of formula (C1), Δ H and t were not detected_max(indicated by "#")

Fig. 4 shows a bar graph of E modulus and Flexural Strength (FS) determined for the cured composition of fig. 3. In fig. 4, E modulus is depicted by dark gray bars and Flexural Strength (FS) is depicted by light gray shaded bars. For compounds of formula (C3) and (C1), the E modulus and flexural strength (indicated by an "@") were not determined due to pre-test failure.

Fig. 5 to 9 show FT-IR spectra before and after the compounds of formulae (Ib) (see fig. 5) and (Ic) (see fig. 6) indicated by the polymerization and the comparative compounds (C2) (see fig. 7), (C3) (see fig. 8) and (C1) (see fig. 9). In each of fig. 5 to 9, the lower spectrum was recorded before polymerization and the upper spectrum was recorded after polymerization.

Detailed Description

The terms "polymerization" and "polymerizable" refer to the formation of larger molecules, i.e., a combination of macromolecules or polymers, by covalently bonding a plurality of smaller molecules, such as monomers. The monomers may combine to form only linear macromolecules or they may combine to form three-dimensional macromolecules, which are commonly referred to as crosslinked polymers. For example, monofunctional monomers form linear polymers, while monomers with at least two functional groups form crosslinked polymers, also referred to as networks. At higher conversion of polymerizable monomers, the amount of multifunctional monomer can be reduced or leaching problems can be mitigated.

The term "(E) or (Z) isomer" as used herein means that in the formulae (II), (III), (IV) and (V), the substituents whose bonds are illustrated in the form of zigzag lines may be in the (E) or (Z) configuration. (E) Or (Z) configuration is determined as follows. First, priorities are assigned to all substituents bonded to a carbon-carbon double bond according to the cahn-lngold-prelog priority rule with well-defined meaning in the field of organic chemistry. Next, the configuration of the substituent group whose bond is described in the form of a zigzag line is determined with respect to the substituent group located at the adjacent carbon atom of the carbon-carbon double bond. For example, a substituent whose bond is illustrated in the form of a zigzag line may be in the (E) position, i.e., on the opposite side of the double bond from the substituent located at the adjacent carbon of the carbon-carbon double bond and having the highest priority here (trans configuration). Alternatively, the substituents whose bonds are illustrated in the form of zigzag lines may be in the (Z) position, i.e., on the same side of the double bond as the substituent located at the adjacent carbon of the carbon-carbon double bond and having the highest priority here (cis configuration).

The terms "cure" and "photocure" mean that the functional oligomers and monomers or even polymers polymerize into a crosslinked polymer network. Curing is the polymerization of unsaturated monomers or oligomers in the presence of a crosslinking agent.

"actinic radiation" is any electromagnetic radiation capable of producing photochemical effects and may have a wavelength of at least 150nm and up to and including 1250nm, and typically at least 300nm and up to and including 750 nm.

The term "sensitizer" is any compound that forms free radicals when activated, for example, by exposure to light or interaction with a co-initiator in a photochemical process.

The term "coinitiator" refers to a molecule that produces a chemical change in another molecule, such as a photosensitizer, during a photochemical process. The co-initiator may be a sensitizer or an electron donor.

The term "electron donor" as used herein means a compound capable of donating an electron in a photochemical process. Suitable examples include organic compounds having heteroatoms with lone electron pairs, such as amine compounds.

The present invention provides polymerizable dental compositions that are polymerizable or copolymerizable by free radical polymerization. The polymerizable dental composition may be a dental material intended for use in the oral cavity. Preferably, the polymerizable dental composition of the present invention is selected from the group consisting of dental adhesives, dental primers, dental resin-modified glass ionomer cements, pit and fissure sealants, dental composites and dental flow agents. The dental composition may be cured by irradiation with actinic radiation.

Polymerizable compounds of the formula (I)

The polymerizable dental composition of the present invention comprises a polymerizable compound of formula (I). The polymerizable dental composition can include one or more polymerizable compounds of formula (I).

The polymerizable dental composition of the present invention comprises the polymerizable compound of formula (I) in an amount of 1 to 70 weight percent based on the total weight of the polymerizable dental composition. Preferably, the polymerizable dental composition comprises one or more compounds of formula (I) in an amount of from 10 to 60 weight percent, most preferably from 20 to 60 weight percent, based on the total weight of the entire polymerizable dental composition.

The amount of the compound of the formula (I) may be appropriately selected in view of the intended use. For example, the dental adhesive may comprise 1 to 70 weight percent, preferably 20 to 60 weight percent, based on the total weight of the entire polymerizable dental composition. The dental primer may comprise 1 to 70 weight percent, preferably 5 to 25 weight percent, based on the total weight of the entire polymerizable dental composition. The socket sealant can comprise 1 to 70 weight percent, preferably 5 to 20 weight percent, based on the total weight of the entire polymerizable dental composition. The dental glass ionomer cement may comprise 1 to 30 weight percent, preferably 2 to 10 weight percent, based on the total weight of the entire polymerizable dental composition.

(a) The polymerizable compound has the following formula (I):

X'-L-X"

(I)。

in formula (I), X' is a specific polymerizable group linked to the group X "by a divalent linking group L. The group X "may be polymerizable.

According to the invention, X' is a group of formula (II) or (III):

in formulae (II) and (III), the dotted line represents a double or triple bond, preferably a double bond. In the presence of a triple bond, R is absent⁴And R⁵。

The jagged lines indicate that formulas (II) and (III) comprise any of the (E) or (Z) isomers. In the case where the dotted line in formula (III) represents a triple bond, then in the portion CR⁴＝CR⁵There is no (E) or (Z) isomerism.

In particular, in the formulae (II) and (III), R¹May be in either the (E) or (Z) configuration, for example, relative to the carbonyl group. In addition, if CR⁴And CR⁵The bond between is a double bond, then sawThe dentate lines/lines may be in either (E) or (Z) configuration, e.g. with respect to the partial-CHR³-in said configuration. Preferably, the substituent (which is R) having the highest priority relative to the adjacent carbon atom of the carbon-carbon double bond according to the Cahn-lngold-Prelog priority rule²Or carbonyl group), R¹In (E) configuration. In addition, if CR⁴And CR⁵Is a double bond, it is preferred that the substituent bonded to the carbon-carbon double bond via the jagged line/bond is of higher priority than the substituent R⁵A substituent higher and having the highest priority according to the cahn-lngold-prelog priority rule (which is R) relative to the adjacent carbon atom of the carbon-carbon double bond⁴Or part-CHR³) Said jagged lines/keys are in (E) configuration.

Thus, any compound of formula (I) is represented by formula (II) and/or (V) (meth) acryloyl or formula (III) and/or (VI) reverse (meth) acryloyl and the adjacent moiety-CHR³The double or triple bond of the hydrogen atom of (E) -which confers acidity on the C-H. Without wishing to be bound by theory, it is believed that this C-H acidity in combination with the polymerizable C-C double bond of the (reverse) (meth) acryloyl group provides a particularly advantageous enthalpy of polymerization and viscosity of the compound of formula (I). In addition, due to the C — H acidity described above, the compounds of formula (I) provide an advantageous maximum polymerization rate and desirable mechanical properties, such as flexural strength.

The C-H acidity may be impaired by internal and external N-allyl groups. It has been unexpectedly found that the moiety-CHR³The C-H acidity of the hydrogen atoms of (A) is less prone to be impaired by internal and external N-allyl groups, for example when determined by CR⁴And CR⁵When the double or triple bond represented together is located between Z ═ N-R and Z ═ N-R'. Thus, in order to provide an advantageous CH acidity, in formula (I) according to the invention, the above double or triple bond is located between Z ' and Z, which may form an N-allyl group when Z ' and Z represent N-R and Z ═ N-R '.

In the prior art EP 2895138A 1, there is no general teaching of the position of the C-C double bond in the linking group of the polymerizable compound, since the effect of C-H acidity explained above is not recognized. In contrast, EP 2895138 a1 teaches that the allyl group must be bound compulsorily to the nitrogen of the polymerizable (meth) acrylamide unit for enabling an advantageous cyclopolymerization reaction.

R of the formulae (II) and (III)¹And R²May be the same or different, and independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which may be substituted with at least one moiety selected from the group consisting of hydroxyl, alkoxy, and acidic groups.

R of the formulae (II) and (III)³Represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which may be substituted with an alkoxy or acidic group.

R of the formulae (II) and (III)⁴And R⁵May be the same or different, and independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which groups may be substituted with alkoxy or acidic groups.

R of the formulae (II) and (III)⁶Represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which groups may be substituted by alkoxy groups.

Z' and Z ", which may be the same or different, independently represent an oxygen atom, a sulfur atom or > N-R, wherein R is a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which groups may be substituted with alkoxy or acidic groups. Alternatively, R is a group of formula (IV):

preferably, Z 'and/or Z' represent>N-R, wherein R represents a group of formula (IV), most preferably wherein R represents¹¹、R¹²、R¹³And R¹⁴The radical of formula (IV) representing a hydrogen atom, i.e. the radical (IV) is an unsubstituted allyl radical. Thus, the group of formula (IV) or allyl may be reacted with a (meth) acryloyl group of formula (II)The radicals or the polymerizable carbon-carbon double bonds of the reverse (meth) acryloyl group of formula (III) together participate in the ring polymerization reaction according to scheme 1 below:

scheme 1: intramolecular cyclisation polymerisation of a compound of formula (I) wherein X ═ a group of formula (II) wherein Z ═ a>N-R, wherein R is a group of formula (IV) wherein R is¹¹＝R¹²＝R¹³＝R¹⁴Hydrogen atom.

The ring formation by means of the above cyclopolymerization can be verified, for example, by means of infrared spectroscopy (IR) alone or in combination with another analytical method, for example nuclear magnetic resonance spectroscopy (NMR).

Intramolecular cyclization polymerization of N-allyl acrylamide is known in the chemical art and is described, for example, by l.trosasarelli et al in "radical polymerization of non-conjugated dienes: N-Allylacrylamide in methanol (Free radial Polymerization of Unconated Dienes: III.N-Allylacrylamide in methanol), "Macro chemical (Die Makromolekulare Chemie)," 1967, Vol.100, p.147 to 155, or W.Fukuda, "Cyclopolymerization of N-Alkyl-N-Allylacrylamide" (Polymer Journal), 1988, Vol.20, p.4, p.337 to 344.

Without wishing to be bound by theory, the above-described cyclopolymerization may cause a reduction in the number of polymerizable network forming points, i.e. a reduction in the crosslinking density, compared to compounds of formula (I) which do not have the group R in the form of an alkylene group, such as the group of formula (IV). This in turn may provide a reduction in the polymerization stress compared to a similar compound of formula (I) having the same molar mass and the same amount of polymerizable double bonds, but without the group Z' and/or Z "being > N-R, wherein R represents a group of formula (IV), in particular an allyl group.

The jagged lines indicate that formula (IV) includes any of the (E) or (Z) isomers. In particular, R¹¹May be in (Z) or (E) configuration, e.g. with respect to part CR¹³R¹⁴In the configuration described. Preferably, the substituent (which may be R) having the highest priority according to the Carn-Engell-Prerogue priority rule with respect to the adjacent carbon atom at the carbon-carbon double bond¹²Or part of CR¹³R¹⁴)，R¹¹In (E) configuration.

R of the formula (IV)¹¹And R¹²May be the same or different. And independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which may be substituted with an alkoxy or acidic group.

R of the formula (IV)¹³And R¹⁴May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which may be substituted with an alkoxy or acidic group. Or, R of formula (IV)¹³And R¹⁴Taken together represent oxygen atoms which together with adjacent carbon atoms form a carbonyl group.

In formula (I), X "represents a moiety selected from the group consisting of a hydroxyl group, a thiol group, an alkoxy group and an acidic group, or a moiety of the following formula (V) or (VI):

the jagged lines indicate that formula (V) encompasses any of the (E) or (Z) isomers. Specifically, in formula (V), the substituent (which may be R) having the highest priority according to the cahn-lngold-prelog priority rule with respect to the adjacent carbon atom of the carbon-carbon double bond⁸Or carbonyl group), R⁷May be in either (Z) or (E) configuration.

R of the formulae (V) and (VI)⁷And R⁸May be the same or different, and independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which may be substituted with at least one group selected from the group consisting of hydroxy, thioA partial substitution of the group consisting of alcohol groups, alkoxy groups and acid groups.

R of the formulae (V) and (VI)⁹Represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which may be substituted with an alkoxy or acidic group.

R of the formulae (V) and (VI)¹⁰Represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which groups may be substituted by alkoxy groups.

Z and Z of formulae (V) and (VI), which may be the same or different, independently represent an oxygen atom, a sulfur atom or > N-R ', wherein R' is a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which groups may be substituted with alkoxy or acidic groups. Alternatively, R ' is a group of formula (IV) as defined for R of Z ' and Z "of formulae (II) and (III), and is independently selected from R of Z ' and Z" of formulae (II) and (III). Preferably, R' of formulae (V) and (VI) has the same formula (IV) as R of formulae (II) and (III).

Preferably, Z and/or Z represents>N-R ', wherein R' represents a group of formula (IV), most preferably wherein R¹¹、R¹²、R¹³And R¹⁴The radical of formula (IV) representing a hydrogen atom, i.e. the radical (IV) is an unsubstituted allyl radical. Thus, the group of formula (IV) or allyl group may participate in the cyclopolymerization reaction, as described above in connection with Z' and Z ", together with the polymerizable carbon-carbon double bond of the methacryloyl group of formula (IV) or of the inverse methacryloyl group of formula (V).

The groups "> N-R" and "> N-R '", as defined in relation to Z ' and Z ", refer to tertiary amine groups, wherein the residue R or R ' is bonded to the nitrogen atom in formulae (II), (III), (V) and (VI) via the two bonds/valencies indicated by" > ". Alternatively, instead of "> N-R" and "> N-R '", the referents "-N (-R) -" and "-N (-R') -" may be used.

R for formulae (II) and (III)¹、R²、R³、R⁴、R⁵、R⁶、R、R¹¹、R¹²、R¹³、R¹⁴And R of the formulae (V) and (VI)⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴The "linear, branched or cyclic alkyl or alkenyl group" of R' is not particularly limited. Preferably, the "linear, branched or cyclic alkyl or alkenyl" denotes straight chain C_1-16Or branched or cyclic C_3-8Alkyl or straight-chain C_2-16Or branched or cyclic C_3-8Alkenyl, more preferably represents straight chain C_1-8Or branched or cyclic C_3-6Alkyl or straight-chain C_2-8Or branched or cyclic C_3-6Alkenyl, most preferably represents straight chain C_1-4Or branched or cyclic C_4-6Alkyl or straight-chain C_2-4Or branched or cyclic C_4-6An alkenyl group.

Illustrative examples of straight-chain or branched alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl or hexyl, and illustrative examples of straight-chain or branched alkenyl groups are vinyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, tert-butenyl, sec-butenyl, pentenyl or hexenyl.

R as herein with formulae (II) and (III)¹、R²、R³、R⁴、R⁵、R⁶、R、R¹¹、R¹²、R¹³、R¹⁴And R of the formulae (V) and (VI)⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴The term "alkenyl" used in conjunction with R' means a monovalent group derived from a hydrocarbon having a carbon number as defined above. Preferably, the alkenyl group contains at least one carbon-carbon double bond, more preferably 1 to 3 carbon-carbon double bonds, even more preferably 1 or 2 carbon-carbon double bonds, most preferably one carbon-carbon bond. Furthermore, it is preferred that at least one carbon-carbon double bond of the alkenyl group is located between the second and third carbon atoms adjacent to the first carbon attaching the alkenyl group to the compound of formula (I).

R for the formulae (II) and (III)¹、R²、R³、R⁴、R⁵、R⁶、R、R¹¹、R¹²、R¹³、R¹⁴And R of the formulae (V) and (VI)⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴The most preferred alkenyl groups of R' may be the same or different and are independently selected from the group consisting of: allyl, 1-cyclopropane-1-yl, 2-cyclopropane-1-yl, 1-cyclobutane-1-yl, 2-cyclobutane-1-yl, 1-cyclopentan-1-yl, 2-cyclopentan-1-yl, 3-cyclopentan-1-yl, 1, 3-cyclopenta-1-yl, 2, 4-cyclopenta-1-yl, 1-cyclohexen-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 1, 3-cyclohexadiene-1-yl and 2, 5-cyclohexadiene-1-yl.

R for formulae (II) and (III)¹、R²、R³、R⁴、R⁵、R⁶、R、R¹¹、R¹²、R¹³、R¹⁴And R of the formulae (V) and (VI)⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴The "alkoxy group" defined for R' is not particularly limited. Preferably, the alkoxy group is a straight chain C_1-16Or branched or cyclic C_3-8Alkoxy, more preferably straight chain C_1-8Or branched or cyclic C_3-6Alkoxy, most preferably straight chain C_1-4Or branched or cyclic C_4-6An alkoxy group. C_1-6Illustrative examples of alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclobutoxy, cyclopentyloxy and cyclohexyloxy.

R as herein with formulae (II) and (III)¹、R²、R³、R⁴、R⁵、R⁶、R、R¹¹、R¹²、R¹³、R¹⁴And R of the formulae (V) and (VI)⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴The term "acidic group" used in combination with R' meansAny group which imparts acidity in proton donating ability to the compound of formula (I). Preferably, the acidic groups are independently selected from carboxylic acid groups, sulfonic acid groups, phosphonic acid groups and phosphoric acid monoester groups (-O-P (═ O) (OH)₂)。

The following are preferred groups of the formulae (II) and (III), in which R and R³As defined above:

in formulae (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIIa), (IIIb), (IIIc), (IIId)³Preferably represents a hydrogen atom, and R preferably represents a hydrogen atom; methyl, ethyl or n-propyl, which groups may optionally be substituted by acidic groups; an allyl group; 2-cyclopropane-1-yl; 2-cyclobutane-1-yl; 2-cyclopentan-1-yl; 2, 4-cyclopentadien-1-yl; 2-cyclohexen-1-yl and 2, 5-cyclohexadien-1-yl.

The radicals of the formulae (IIa) and (IIIa) are particularly preferred.

The following are preferred groups of the formulae (V) and (VI) in which R' and R⁹As defined above:

in the formulae (Va), (Vb), (Vc), (Vd), (Ve), (Vf), (VIa), (VIb), (VIc), (VId), R⁹Preferably represents a hydrogen atom, and R' preferably represents a hydrogen atom; methyl, ethyl or n-propyl, which groups may optionally be substituted by acidic groups; an allyl group; 1-cyclopropane-3-yl; 1-cyclobutane-3-yl; 1-cyclopentan-3-yl; 1, 3-cyclopentadien-5-yl; 1-cyclohexen-3-yl and 1, 4-cyclohexadien-6-ylAnd (4) substitution.

The radicals of the formulae (Va) and (VIa) are particularly preferred.

Preferably, if X 'of the compound of formula (I) represents a group of formula (II), then X' represents a group of formula (V), and if X 'represents a group of formula (III), then X' represents a group of formula (VI).

Preferably, R of the formulae (II) and (III) and/or R' of the formulae (V) and (VI)¹³And R¹⁴Taken together represent oxygen atoms which together with adjacent carbon atoms form a carbonyl group.

In formula (I), instead of the residue R as described above for¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰、R'、R¹¹、R¹²、R¹³And R¹⁴Any two of these residues may form a ring together with the bridging atom to which the residue is attached. In particular, R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰R' and, if present, R¹¹、R¹²、R¹³And R¹⁴May together represent an alkylene or alkenylene group which may be substituted by an alkoxy group and an acidic group or-NR^▲R^▼Is substituted by radicals in which R^▲And R^▼Independently of one another, represents a hydrogen atom or an alkyl group.

Or, R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰R' and, if present, R¹¹、R¹²、R¹³And R¹⁴Any two residues in (a) that are not geminal or vicinal groups may together represent a single bond.

The single bond described above or the optionally substituted alkylene or alkenylene described above may form a 3-to 8-membered saturated or unsaturated ring together with the bridging atom to which the residue is attached, wherein the polymerizable compound of formula (I) may include one or more of the 3-to 8-membered saturated or unsaturated rings.

And the residue R described above¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰、R'、R¹¹、R¹²、R¹³And R¹⁴The "alkoxy" which may be substituted for the alkylene or alkenylene formed by two of these residues, the rings of any two of which form a bond, is preferably C_1-6An alkoxy group; more preferably C_1-3Alkoxy, such as methoxy, ethoxy, n-propoxy or isopropoxy; and is-NR^▲R^▼The "alkyl" group of the radical "is preferably C_1-6An alkyl group; more preferably C_1-3Alkyl groups such as methyl, ethyl, n-propyl or isopropyl.

The phrase "if present, R" as used herein¹¹、R¹²、R¹³And R¹⁴"means if Z' or Z" represents wherein R is of formula (IV)>N-R and/or for Z or Z, wherein R' is of formula (IV)>N-R' then R of the residue formula (IV)¹¹、R¹²、R¹³And R¹⁴Can be reacted with R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰Either of R' forms a ring as described above. However, it is readily understood that R represented by formula (IV) cannot form a ring with itself, i.e. cannot form a ring with its residue R¹¹、R¹²、R¹³And R¹⁴Forming a ring. The same applies to R' represented by formula (IV).

The term "geminal group" as used herein means that two residues are bonded to the same atom.

The term "vicinal group" as used herein means that two residues are bonded to adjacent atoms, respectively.

Preferably, in formula (II) or (III) of the compound of formula (I), R¹、R²、R³、R⁴、R⁵、R⁶Any two of R may together represent an alkylene or alkenylene group which together with the bridging atom to which the residue is attached forms a 3-to 8-membered saturated or unsaturated ring, wherein the alkylene or alkenylene group may be substituted by an alkoxy group, an acidic group or-NR^▲R^▼Is substituted by radicals in which R^▲And R^▼Independently of one another, represents a hydrogen atom or an alkyl group.

Likewise, with respect to the compounds of formula (I) of formula (V) or (VI), preferably R⁷、R⁸、R⁹、R¹⁰Any two residues of R' may together represent an alkylene or alkenylene group which together with the bridging atom to which the residue is attached forms a 3-to 8-membered saturated or unsaturated ring, wherein the alkylene or alkenylene group may be substituted by an alkoxy group, an acidic group or-NR^▲R^▼Is substituted by radicals in which R^▲And R^▼Independently of one another, represents a hydrogen atom or an alkyl group.

In addition to the preferred ring formation described above with respect to formulae (II) or (III) and (V) or (VI), residues that are not geminal or vicinal groups may together represent a single bond that together with the bridging atom to which the residue is attached forms a 3-to 8-membered saturated or unsaturated ring. In particular, the residue R¹、R²Or R⁶Residue R with Z³、R⁴、R⁵And any of R together, the residue R⁷、R⁸Or R¹⁰R with Z⁹Or R' together, or a residue R³And R⁹，R⁴And R⁹，R¹¹And R¹³Or R¹⁴May together form a single bond that together with the bridging atom to which the residue is attached forms a 3-to 8-membered saturated or unsaturated ring.

More preferably, in formula (I), one or more rings are formed within formula (II)/(III) and/or formula (V)/(VI), wherein the formation in formula (II) or (III) is preferredOne ring and forms a ring in formula (V) or (VI). In particular, any two residues R in the formula (II) or (III)¹、R²、R³、R⁴、R⁵、R⁶R and/or any two residues R of formula (V) or (VI)⁷、R⁸、R⁹、R¹⁰And R' may together represent an alkylene or alkenylene group which together with the bridging atom to which the residue is attached forms a 3-to 8-membered saturated or unsaturated ring, wherein the alkylene or alkenylene group may be substituted by an alkoxy group, an acidic group or-NR^▲R^▼Is substituted by radicals in which R^▲And R^▼Independently of one another, represents a hydrogen atom or an alkyl group.

Furthermore, instead of or in addition to the more preferred ring formation within formulae (II)/(III) and (V)/(VI) described above, a ring may be formed between the residue of formula (II)/(III) and the residue of formula (V)/(VI). In particular, the residue R¹、R²Or R⁶Residues R which may be substituted with Z³、R⁴、R⁵And any one of R together represents a single bond or an optionally substituted alkylene or alkenylene group as described above, wherein the residue together with the bridging atom to which it is attached forms a 3-to 8-membered saturated or unsaturated ring.

In the compounds of formula (I), L may or may not be present. When present, L represents a divalent linking group, and when absent, X' and X "are directly bonded by a single bond.

Preferably, L is a group of formula (VII)

In formula (VII), m, n and o, which may be the same or different, are integers of 0 to 3; and p is 0,1 or 2. Preferably, p is 0 or 1. Further, n is preferably 0. For m and o, it is preferred that m or o be 0. Preferably, in formula (VII), m is 0, n is 0 or 1, and o is 0 to 3, more preferably, m is 0, n is 0 or 1, and o is 0 or 1. Most preferably, in formula (VII), m ═ n ═ o ═ 0, i.e., L is absent and X' and X ″ are bonded directly by a single bond.

The compounds of formula (I) can be prepared, for example, readily by means of the synthetic route as shown in scheme 2:

and (2) a flow scheme: exemplary synthetic routes for preparing Compounds of formula (I)

In scheme 1, a synthetic route for the preparation of compounds of formula (I) is schematically depicted, wherein X' represents a group of formula (II) wherein R¹、R²、R³、R⁴And R⁵Is a hydrogen atom, X' represents a group of formula (V) wherein R⁷、R⁸And R⁹Is a hydrogen atom, R' and R are the same, and L is a single bond. X and X' represent suitable leaving groups which may for example be halogen, such as Cl, Br, I, alkoxy, hydroxy, alkyl-or aryl-sulfonates, such as methanesulfonate, tosylate and triflate, and X "may be a halogen atom, such as Cl, Br and I. It is understood that, instead of the radical R, a radical R is substituted¹、R²、R³、R⁴、R⁵、R⁷、R⁸And R⁹Represents a hydrogen atom, these groups may vary and may also represent residues other than a hydrogen atom, i.e. as defined above for the groups. Furthermore, it is to be understood that in order to obtain R therein¹And R⁷Is different and/or R³And R⁸Different and/or R and R ' are different, one of the leaving groups X and X ' may suitably be protected or two leaving groups X and X ' with different reactivity may be provided. Then, in the formula H₂N-R first amine compound and first (meth) acrylic acid derivative X ″ -C (═ O) -CR₂＝CHR₁After the subsequent reaction, the protected leaving group X or X' may be deprotected or, alternatively, rendered substantially non-reactive with less reactivityThe corresponding leaving group X or X' is reacted with a compound of the formula H₂N-R' second amine compound and second (meth) acrylic acid derivative X ″ -C (═ O) -CR₈＝CHR₇And (4) reacting. The protecting group or Groups of (optionally) the protected leaving group X or X 'or of different reactivity are not particularly limited and may be any conventional protecting group, as described, for example, in p.g.m.wuts and t.w.greene, Protective Groups in Organic Synthesis in greens (Greene's Protective Groups in Organic Synthesis), 4 th edition, John Wiley parent publishing company (John Wiley and Sons Inc.), 2007.

Particularly preferred are compounds of formula (I) wherein L represents a single bond and CR⁴And CR⁵The dotted line in between represents a double bond, while X 'represents a group of formula (II) and X "represents a group of formula (V), or X' represents a group of formula (III) and X" represents a group of formula (VI). Furthermore, it is preferred that in such compounds of formula (I) Z represents a group N-R and Z 'represents a group N-R'.

Most preferably, in the compounds of formula (I), R of formula (II) and (III)¹、R²、R³、R⁴、R⁵、R⁶、R¹¹、R¹²、R¹³、R¹⁴Z ', Z' and R of the formulae (V) and (VI)⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴Z and Z are selected in the same way.

Preferably, the residues R and R⁴And/or residues R' and R⁵May together represent a single bond, alkylene or alkenylene that together with the bridging atom to which the residue is attached forms a 3-to 6-membered saturated or unsaturated ring. This ring may be in the form of 1H-aziridine-1, 3-diyl, 1-azetidine-1, 3-diyl, 1-pyrroline-1, 4-diyl, 2-pyrroline-1, 4-diyl, 1, 2-dihydropyridine-1, 5-diyl, 2, 3-dihydropyridine-1, 5-diyl or 3, 4-dihydropyridine-1, 5-diyl, more preferably 1-pyrroline-1, 4-diyl, 2-pyrroline-1, 4-diyl, 1, 2-dihydropyridine-1, 5-diyl, 2, 3-dihydropyridine-1, 5-diyl or 3, 4-dihydropyridine-1, 5-diylForm (a). Preferred rings are in the form of 4-to 6-membered saturated or unsaturated rings in the form of 1-pyrroline-1, 4-diyl, 2-pyrroline-1, 4-diyl, 1, 2-dihydropyridine-1, 5-diyl, 2, 3-dihydropyridine-1, 5-diyl or 3, 4-dihydropyridine-1, 5-diyl, more preferably in the form of 1-pyrroline-1, 4-diyl, 2-pyrroline-1, 4-diyl, 1, 2-dihydropyridine-1, 5-diyl, 2, 3-dihydropyridine-1, 5-diyl or 3, 4-dihydropyridine-1, 5-diyl. Most preferred is 3, 4-dihydropyridine-1, 5-diyl. Furthermore, it is preferred that the residues R and R are substituted by⁴And residues R' and R⁵The same ring is formed together with the bridging atom to which it is attached.

In place of the residues R and R described above⁴And/or residues R' and R⁵In formula (I), the residue R³And R⁹Or a residue R⁴And R⁹May together represent a single bond, alkylene or alkenylene that together with the bridging atom to which the residue is attached forms a 3-to 8-membered saturated or unsaturated ring, with 3-to 6-membered unsaturated rings having one or two carbon-carbon double bonds being preferred. Preferably, the residue R³And R⁹Or a residue R⁴And R⁹Together with L representing a single bond or an alkylene or alkenylene group, form an unsaturated ring selected from the group consisting of cyclobuten-diyl, cyclopenten-diyl, cyclohexene-diyl and cyclohexadiene-diyl, wherein R⁴And R⁹Three-membered rings in the form of cyclopropene-diyl groups may also be formed.

In place of the residues R and R described above⁴The residues R' and R⁵A residue R³And R⁹And a residue R⁴And R⁹Or in addition to said ring formation, if present, R¹¹、R¹²、R¹³And R¹⁴Any two residues in (a) may form a ring. Preferably, R is¹¹Can be reacted with R¹³Or R¹⁴Together represent a single bond or an alkylene or alkenylene group which together with the bridging atom to which they are attached form a 3-to 8-membered saturated or unsaturated ring, with preference being given to forming a 3-to 6-membered unsaturated ring having one or two carbon-carbon double bonds. Most preferably, R¹¹And R¹³Or R¹⁴Together with the bridging atom to which they are attached form a 1-cyclopropene-3-yl, 1-cyclobuten-3-yl, 1-cyclopenten-3-yl, 1, 3-cyclopenten-5-yl, 1-cyclohexen-3-yl, and 1, 4-cyclohexadien-6-yl group.

For example, the compound of formula (I) may have the following structural formula, wherein R³、R⁶、R⁹、R¹⁰R, R', Z ", Z and o have the same meaning as defined above:

preferably, the compound of formula (I) has the following structural formula:

more preferably, the compound of formula (I) has the following structural formula:

most preferred is

Preferably, the polymerizable compound of the following formula (I) has a refractive index in the range of 1.500 to 1.580.

Preferably, the dental composition according to the invention does not contain an acrylic amide compound of the following formula (a):

wherein R, R^◆And R^◆◆May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl group, which groups may be substituted with acidic groups; r^#And R^##The same or different, independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group which may be substituted with an acidic group, preferably R^#And R^##Represents an alkenyl group, more preferably an allyl group, and R_LDenotes a divalent linking group in the form of an alkenylene radical, preferably C₂To C₂₀Alkenylene, more preferably C₂To C₂₀Alkenylene, wherein the carbon-carbon double bond is located between the second and third carbon atoms of the alkenylene in which the first carbon atom is bonded to any one of the nitrogen atoms of the compound of formula (a).

Most preferably, the dental composition according to the invention is free of compounds of formula (a) in the form of N, N' -diallyl-1, 4-bisacrylamido- (2E) -but-2-ene (BAABE) and/or N, N "-diallyl-1, 4-bismethacrylamido- (2E) -but-2-ene having the following structural formula:

(b) photosensitive agent

The polymerizable dental composition according to the present invention further comprises (b) a photosensitizer. The polymerizable dental composition can include (b) one or more sensitizers. The sensitizer is different from an iodide salt.

The sensitizer is not particularly limited. Preferably, the sensitizer may be selected from Norrish (Norrish) type I sensitizers and Norrish type II sensitizers.

Norrish type I sensitizers are compounds that undergo excitation by energy absorption, wherein the compounds subsequently decompose into one or more free radicals (norrish type I). Typical norrish type I sensitizers are for example phosphine oxides.

Norrish type II sensitizers are compounds that undergo excitation and the excited sensitizer compound interacts with a second compound through an energy transfer or redox reaction to form a free radical from either compound. Typical norrish type II sensitizers are diketones, such as 1, 2-diketones.

The sensitizer may be selected from 1, 2-diketones, phosphine oxides and acylsilanes or acylgermanium compounds.

Preferably, suitable phosphine oxide sensitizers are selected from the group consisting of: 2, 4-6-trimethylbenzoyl-diphenylphosphine oxide(s) (II)TPO), 2, 4-6-trimethylbenzoyl-diphenyl phosphonite salt(s) ((s)TPO-L, TPO-L), bis (2, 4-6-trimethylbenzoyl) -phenylphosphine oxide ((II)BAPO-X). More preferably, the phosphine oxide sensitizer is 2, 4-6-trimethylbenzoyl-diphenylphosphine oxide(s) ((II))TPO)。

Preferably, examples of suitable 1, 2-diketones are selected from the group consisting of: camphorquinone, benzil, 2' -3,3' -and 4,4' -dihydroxybenzol, 2, 3-butanedione, 2, 3-pentanedione, 2, 3-hexanedione, 3, 4-hexanedione, 2, 3-heptanedione, 3, 4-heptanedione, 2, 3-octanedione, 4, 5-octanedione difuranoyl, diacetyl, 1, 2-cyclohexanedione, 1, 2-naphthoquinone, and acenaphthoquinone (acenaphtoquinone). Examples of suitable 1, 3-diketones are dibenzoylmethane, benzoylacetone and acetylpropionyl methane. Preferably, the diketone sensitizer is camphorquinone.

Further, the sensitizer may be an acylsilane or acylgermanium compound having the following formula (VIII):

X^#-R^#

(VIII)

wherein

X^#Is a group of formula (IX):

wherein

M is Si or Ge;

R¹⁵represents a substituted or unsubstituted hydrocarbon group or a hydrocarbonyl group;

R¹⁶represents a substituted or unsubstituted hydrocarbon group or a hydrocarbonyl group;

R¹⁷represents a substituted or unsubstituted hydrocarbon group; and is

R^#(i) Having a reaction with X^#The same meaning, whereby the compound of formula (VIII) may be symmetrical or asymmetrical; or

(ii) Is a group of formula (X):

wherein

R¹⁸Represents a substituted or unsubstituted hydrocarbyl, trihydrocarbylsilyl, mono (hydrocarbylcarbonyl) dihydrocarbylsilyl or di (hydrocarbylcarbonyl) monohydrocarbylsilyl group; and is

Y represents a single bond, an oxygen atom or a group NR¹⁹Wherein R is¹⁹Represents a substituted or unsubstituted hydrocarbon group;

or

(iii) When M is Si, R^#May be a substituted or unsubstituted hydrocarbon group.

It has surprisingly been found that the compounds of formula (VIII) represent polymerization initiators which are particularly suitable for dental compositions. In the case of using the compound of the formula (VIII), high polymerization efficiency is obtained and no coloring problem occurs, or coloring is suppressed efficiently in a polymerization system including a conventional sensitizer such as camphorquinone. Furthermore, the light absorption of the compounds of formula (VIII) is in the wavelength range that is typically used in dental applications, the compounds are compatible with the ingredients of the dental composition, and furthermore, the compounds are considered physiologically harmless.

In combination with a compound of formula (VIII), the term "substituted" as used herein means R¹⁵、R¹⁶、R¹⁷、R¹⁸And R¹⁹May be substituted with a substituent selected from the group consisting of: halogen atom, nitro group, cyano group, hydroxy group, amino group, C_1-6Alkyl radical, C_1-6Alkoxy and-NR^xR^yGroup, wherein R^xAnd R^yIndependently of one another represent C_1-6An alkyl group. Here, illustrative examples of the halogen atom may be fluorine, chlorine, bromine and iodine. C_1-6Alkyl is, for example, methyl, ethyl, n-propyl, isopropyl and n-butyl. C_1-6Illustrative examples of alkoxy groups are, for example, methoxy, ethoxy and propoxy. The alkyl portion of these substituents may be straight chain, branched chain or cyclic. Preferably, the substituents are selected from chlorine atoms, nitro groups, C_1-4Alkoxy and-NR^xR^yGroup, wherein R^xAnd R^yIndependently of one another represent C_1-4An alkyl group.

If R is¹⁵、R¹⁶And R¹⁷Is substituted, it is then preferably substituted by 1 to 3And (b) a substituent, more preferably 1 substituent.

In the compounds of formula (VIII), the moiety R¹⁵、R¹⁶And R¹⁷The following can be defined:

R¹⁵and R¹⁶Independently of one another, represents a substituted or unsubstituted hydrocarbon group or a hydrocarbon-based carbonyl group, and R¹⁸Represents a substituted or unsubstituted hydrocarbon group.

R¹⁹Having a structure as defined for R¹⁷The same meaning is defined and independently selected therefrom.

The hydrocarbyl group may be an alkyl, cycloalkyl, cycloalkylalkyl, arylalkyl, or aryl group.

The alkyl group may be straight or branched C_1-20Alkyl, usually C_1-8An alkyl group. C_1-6Examples of the alkyl group may include a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, and n-hexyl.

Cycloalkyl may be C_3-20Cycloalkyl radicals, usually C_3-8A cycloalkyl group. Examples of the cycloalkyl group may include those having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Cycloalkylalkyl groups may have 4 to 20 carbon atoms, and may comprise a combination of a straight or branched chain alkyl group having 1 to 6 carbon atoms and a cycloalkyl group having 3 to 14 carbon atoms. Examples of cycloalkylalkyl (-), can for example comprise methylcyclopropyl (-), methylcyclobutyl (-), methylcyclopentyl (-), methylcyclohexyl (-), ethylcyclopropyl (-), ethylcyclobutyl (-), ethylcyclopentyl (-), ethylcyclohexyl (-), propylcyclopropyl (-), propylcyclobutyl (-), propylcyclopentyl (-).

Arylalkyl (-) can be C_7-20Arylalkyl (-), typically having from 1 to 6 carbon atomsA combination of a linear or branched alkyl group and an aryl (-) group having 6 to 10 carbon atoms. Specific examples of arylalkyl (-), are benzyl (-), or phenethyl (-).

The aryl group may comprise an aryl group having 6 to 10 carbon atoms. Examples of aryl groups are phenyl and naphthyl.

R¹⁵And R¹⁶The hydrocarbyl carbonyl group of (A) represents an acyl group (R)_org- (C ═ O) -), in which the organic residue R is_orgIs a hydrocarbyl residue as defined above.

The compounds of formula (VIII) may contain one or two hydrocarbyl carbonyl groups, i.e. R¹⁵Or R¹⁶Any of (A) is hydrocarbyl carbonyl, or R¹⁵And R¹⁶Both are hydrocarbyl carbonyl groups. Preferably, the compound of formula (VIII) contains one hydrocarbyl carbonyl group.

Preferably, the hydrocarbyl carbonyl group is an arylcarbonyl group, more preferably a benzoyl group.

Preferably, R is¹⁵And R¹⁶Independently selected from the group consisting of: straight or branched C_1-6Alkyl and phenyl or benzoyl, which may optionally be substituted by one to three atoms selected from halogen, nitro, C_1-4Alkoxy and-NR^xR^ySubstituent of the group, wherein R^xAnd R^yIndependently of one another represent C_1-4Alkyl, and R¹⁷Is straight or branched C_1-6Alkyl or phenyl.

Most preferably, R¹⁵And R¹⁶Independently selected from the group consisting of: straight or branched C_1-4Alkyl and phenyl or benzoyl, which may optionally be substituted by one or more substituents selected from the group consisting of halogen atoms, nitro, C_1-4Alkoxy and-NR^xR^ySubstituted by a substituent of the group consisting of R^xAnd R^yIndependently of one another represent C_1-4Alkyl, and R¹⁷Is straight or branched C_1-4An alkyl group.

In the compound of formula (VIII), R^#May have a structure of formula (I) with X^#The same meaning, whereby the compounds of formula (VIII) can be symmetrical or asymmetrical. Or, R^#May represent a substituted or unsubstituted hydrocarbon group, or a group of formula (X). Preferably, if R is^#Having a reaction with X^#The same meaning, then the compound of formula (VIII) is asymmetric. If R is^#Represents a substituted or unsubstituted hydrocarbyl group, then said hydrocarbyl group has the same meaning as above for R¹⁵The same meaning is defined and independently selected therefrom.

In the radical of formula (X) of the compound of formula (VIII), R¹⁸Represents a substituted or unsubstituted hydrocarbyl, trihydrocarbylsilyl, mono (hydrocarbylcarbonyl) dihydrocarbylsilyl or di (hydrocarbylcarbonyl) monohydrocarbylsilyl group.

If R of formula (X)¹⁸Is a trihydrocarbylsilyl, a mono (hydrocarbonyl) dihydrocarbylsilyl or a di (hydrocarbonyl) monohydrocarbylsilyl group, then each of said hydrocarbyl and hydrocarbonyl groups has a structure as defined for R¹⁵、R¹⁶And R¹⁷The same meaning is defined and independently selected therefrom.

If M is Si in the compound of the formula (VIII), R^#And may also be a substituted or unsubstituted hydrocarbyl group, wherein the hydrocarbyl group has the same meaning as described above for R¹⁷The same meaning is defined and independently selected therefrom.

For example, wherein R^#Having a reaction with X^#The compounds of formula (VIII) having the same meaning and which are themselves symmetrical may have the following structural formula:

for example, wherein R^#Represents a group of formula (X) wherein Y is a bond, an oxygen atom or NR¹⁹Radical and R¹⁸The compound of formula (VIII) representing a substituted or unsubstituted hydrocarbyl group may have the following structural formula:

for example, wherein R^#Represents a group of formula (X) wherein R¹⁸The compound of formula (VIII) representing a trihydrocarbylsilyl group has the following structural formula:

for example, a compound of formula (VIII) wherein M is Si and R represents a substituted or unsubstituted hydrocarbyl group may have the following structural formula:

preferably, the compound of formula (VIII) is selected from the group consisting of:

among them, the compound of formula (VIII) in which M ═ Si is particularly preferred.

Most preferably, the compound of formula (VIII) is selected from the group consisting of:

among them, M ═ Si is particularly preferable.

The compounds of formula (VIII) may be commercially known compounds or may be prepared according to published procedures.

Wherein M is Si and R^#Compounds of formula (VIII) representing substituted or unsubstituted hydrocarbyl groups can be readily prepared, for example, by means of a single-step Pd-catalyzed reaction using disilanes, as described, for example, by Yamamoto k et al, journal of tetrahedral communication (j.tetrahedron Lett.), 1980, volume 21, pages 1653 to 1656:

and (3) a flow path: preparation of acylsilanes

In scheme 3, the reaction is exemplarily depicted with hexamethylsilane as disilane, thereby obtaining a compound of formula (VIII), wherein R¹⁵、R¹⁶And R¹⁷Represents a methyl group. It is to be understood that R¹⁵、R¹⁶And R¹⁷Can be varied by using disilanes having hydrocarbon substituents other than methyl.

Wherein R is^#Represents a group of formula (X) wherein Y is an oxygen atom and R¹⁸Compounds of formula (VIII) representing hydrocarbyl groups may be prepared, for example, by three-step synthesis, as described by Nicewicz d.a. et al in organic synthesis (org.synth.), 2008, 85, pages 278 to 286. In this three-step synthesis, the acetoacetate ester is converted to the azide compound, followed by reaction with a trihydrocarbylsilyltriflate to obtain a trihydrocarbylsilyldiazoacetate, which is finally reacted with potassium peroxydisulfate to give the target compound:

and (4) a flow chart: preparation of silanyl glyoxylic acid esters

In scheme 4, the reaction is exemplarily depicted for obtaining a compound of formula (VIII), whereinR of formula (X)¹⁸Represents a hydrocarbon group in the form of a tert-butyl group. It is to be understood that R¹⁸Can be varied by using acetoacetic esters other than t-butyl acetoacetate.

Alternatively, compounds of formula (VIII) wherein M is Si, R represents a group of formula (X) and Y represents an oxygen atom may be prepared by reacting a silanyl glyoxylate, a terminal alkyne and an aldehyde in ZnI₂And Et₃N, as described by Nicewicz d.a. in american society of chemistry (j.am.chem.soc.), 2005, 127(17), pages 6170 to 6171. Further syntheses of the silanyl glyoxylate compounds are described, for example, by Boyce g.r. et al in journal of organic chemistry (j.org.chem.), 2012, 77(10), pages 4503 to 4515 and by Boyce G.R et al in communication of organic chemistry (org.lett.), 2012, 14(2), pages 652 to 655.

For example, the following compounds of formula (VIII) are known and commercially available, and their Chemical Abstracts (CAS) numbers are given in parentheses: benzoyltriphenylsilane (1171-49-9), benzoyltrimethylsilane (5908-41-8), 1- [ (trimethylsilyl) carbonyl ] -naphthalene (88313-80-8), 1-methoxy-2- [ (trimethylsilyl) -carbonyl ] -benzene (107325-71-3), (4-chlorobenzoyl) (triphenyl) silane (1172-90-3), (4-nitrobenzoyl) (triphenyl) silane (1176-24-5), (methyldiphenylsilyl) phenyl-methanone (18666-54-1), (4-methoxybenzoyl) triphenylsilane (1174-56-7), and tert-butyl butyldimethylsilyl) glyoxylate (852447-17-7).

All compounds of formula (VIII) include a radical of formula (IX)

M, R therein¹⁵、R¹⁶And R¹⁷As defined above. Depending on the choice of M, the group of formula (IX) represents an acylsilane or acylgermane group. Upon exposure to UV-VIS light, the bond between M and the acyl group may be cleaved, therebyThis forms silyl/germyl and acyl radicals as polymerization initiating structures, but in competition with cleavage into radicals, it is possible to form carbene structures:

and (5) a flow chart: carbene formation contrast radical formation

This competition between polymerization-initiated free radical formation and carbene formation is described by El-Roz, m. et al in current trends in polymer science 2011, volume 15, pages 1 to 13.

Further, in which R^#Having a reaction with X^#In the case of compounds of formula (VIII) which have the same meaning or are a group of formula (X), the C-C bond of the 1, 2-dione moiety (-C (═ O) -) can be cleaved to two acyl radicals upon exposure to UV-VIS light. This cleavage of a compound of formula (VIII) is exemplarily shown, wherein R is a group of formula (X) and Y is an oxygen atom, i.e. for glyoxylic acid esters (-O-C ═ O) -C (═ O) -) compounds:

and (6) a flow path: cleavage of the-O-C (═ O) -moiety of glyoxylic esters

Furthermore, in the compounds of the formula (VIII), in R^#Is wherein Y is an oxygen atom and R¹⁸In the case of the compound of formula (X) which is a substituted or unsubstituted hydrocarbon group, there is a third possibility of radical cleavage. That is, intramolecular or intermolecular hydrogen abstraction can occur, wherein hydrogen radicals are abstracted:

scheme 7: hydrogen abstraction (intramolecular or intermolecular)

Both cleavage of glyoxylate groups and hydrogen abstraction mechanisms for sensitizers not containing silicon or germanium, e.g. ethyl phenylglyoxylate (C:)MBF) is known.

For R in the formula^#Having a reaction with X^#Compounds of formula (VIII) of the same meaning or being a group of formula (X), the inventors carried out molecular modelling calculations from which it was possible to exclude Si-C or Ge-C bond cleavage, since the C-C bond of the-C (═ O) -moiety is weaker than the Si-C or Ge-C bond.

The compound of formula (VIII) represents a photosensitizer. In particular, the compounds may act as norrish type I sensitizers and may therefore be used alone or in combination with optional co-initiators.

Preferably, the sensitizer is camphorquinone, 2, 4-6-trimethylbenzoyl-diphenylphosphine oxide(s) ((R))TPO) or compounds of formula (VIII). Most preferably, the sensitizer is a compound of formula (VIII).

The sensitizer acts as a co-initiator with the iodide salt. Examples of iodonium salts have the formula:

wherein R, which may be the same or different, are²⁰Represents an optionally substituted aryl group, and Y^-Is an anion selected from: hexafluoroantimonate, trifluoromethylsulfate, hexafluorophosphate, tetrafluoroborate, hexafluoroarsenate, and tetraphenylborate. In the iodonium salt, R²⁰Preferred is phenyl which may be substituted by 1 to 3 substituents selected from: halogen atom, cyano group, hydroxy group, amino group, C_1-6Alkyl and C_1-6An alkoxy group. C_1-6Alkyl groups are preferred as substituents.

In particular, there is often a synergistic effect when (b) a photosensitizer is combined with an iodide salt as defined above. Preferred iodonium salts include diaryliodonium salts such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate having the formula:

diphenyliodotetrafluoroborate and tolylisopropyliodonium tetrakis (pentafluorophenyl) borate having the formula

And an iodide salt having the formula:

most preferred iodonium salts are diphenyliodonium hexafluorophosphate and (4-methylphenyl) [4- (2-methylpropyl) phenyl ]]Iodonium hexafluorophosphate salt (f)250, a commercial product available from BASF SE).

Additional polymerizable Compounds

The polymerizable dental composition of the present invention may further contain one or more polymerizable compounds having a polymerizable double bond other than the compound of formula (I) in addition to (a) the polymerizable compound of formula (I). Preferably, the one or more compounds having a polymerizable double bond each contain one or two free-radically polymerizable groups.

Preferably, the further compound having a polymerizable double bond is selected from the group of (meth) acrylates.

Suitable (meth) acrylates may be selected from the group of: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate (HEMA), hydroxypropyl acrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-methyl 1,1' - [ (1-methylethylene) bis [4, 1-phenylene oxide (2-hydroxy-3, 1-propanediyl) ] ] ester of 2-acrylic acid, also known as bisphenol A dimethacrylate ("bis-GMA", CAS-Nos. 1565-94-2), 4,6,16 (or 4,6,6,16) -tetramethyl-10, 15-dioxo-11, 14-dioxa-2, 9-diazepan-16-enoic acid 2- [ (2-methyl-1-oxo-2-propen-1-yl) oxy ] ethyl ester (CAS No. 72869-86-4) (UDMA), glycerol monoacrylate and glycerol diacrylate, glycerol monomethacrylate and glycerol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate in which the number of repeating ethylene oxide units varies from 2 to 30, polyethylene glycol dimethacrylate in which the number of repeating ethylene oxide units varies from 2 to 30) may be mentioned in particular triethylene glycol dimethacrylate ("TEGDMA"), (see, Neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, mono-, di-, tri-and tetra-acrylates and methacrylates of pentaerythritol and dipentaerythritol, 1, 3-butanediol diacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, di-2-methacryloyloxyethyl hexamethylene dicarbamate, di-2-methacryloyloxyethyl trimethyl hexamethylene dicarbamate, di-2-methacryloyloxyethyl dimethyl benzene dicarbamate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol and dipentaerythritol, 1, 3-butanediol diacrylate, 1, 6-hexanediol dimethacrylate, di-2-methacryloyloxyethyl hexamethylene dicarbamate, di-2-methacryloyloxyethyl dimethyl benzene dicarbamate, methylene-bis-2-methacryloyloxyethyl-4-cyclohexylcarbamate, bis-2-methacryloyloxyethyl-dimethylcyclohexanedicarbamate, methylene-bis-2-methacryloyloxyethyl-4-cyclohexylcarbamate, bis-1-methyl-2-methacryloyloxyethyl-trimethyl-hexamethylene dicarbamate, bis-1-methyl-2-methacryloyloxyethyl-dimethylbenzenedicarbamate, bis-1-methyl-2-methacryloyloxyethyl-dimethylcyclohexyldicarbamate, methylene-bis-1-methyl-2-methacryloyloxyethyl-4-cyclohexylcarbamate, bis-2-methacryloyloxyethyl-methyl-4-cyclohexylcarbamate, bis-methyl-2-methacryloyloxyethyl-methyl-4-cyclohexylcarbamate, bis-2-methacryloyloxyethyl-methyl-2-methyl-cyclohexylcarbamate, bis-2-methyl, Bis-1-chloromethyl-2-methacryloyloxyethyl-hexamethylene dicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-trimethylhexamethylene dicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylbenzene dicarbamate, bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylcyclohexane dicarbamate, methylene-bis-2-methacryloyloxyethyl-4-cyclohexyl carbamate, bis-1-methyl-2-methacryloyloxyethyl-hexamethylene dicarbamate, bis-1-methyl-2-methacryloyloxyethyl-trimethylhexamethylene dicarbamate Esters, di-1-methyl-2-methacryloyloxyethyl-dimethylbenzenedicarbamate, di-1-methyl-2-methacryloyloxyethyl-dimethylcyclohexanedicarbamate, methylene-bis-1-methyl-2-methacryloyloxyethyl-4-cyclohexylcarbamate, di-1-chloromethyl-2-methacryloyloxyethyl-hexamethylenedicarbamate, di-1-chloromethyl-2-methacryloyloxyethyl-trimethylhexamethylenedicarbamate, di-1-chloromethyl-2-methacryloyloxyethyl-dimethylbenzenedicarbamate, di-1-methyl-ethyl-N-methyl, Bis-1-chloromethyl-2-methacryloyloxyethyl-dimethylcyclohexane dicarbamate, methylene-bis-1-chloromethyl-2-methacryloyloxyethyl-4-cyclohexylcarbamate, 2' -bis (4-methacryloyloxyphenyl) propane, 2' -bis (4-acryloyloxyphenyl) propane, 2' -bis [4 (2-hydroxy-3-methacryloyloxy-phenyl) ] propane, 2' -bis [4 (2-hydroxy-3-acryloyloxy-phenyl) propane, 2' -bis (4-methacryloyloxyethoxyphenyl) propane, 2' -bis (4-acryloyloxyethoxyphenyl) propane, dimethylcyclohexylcarbamic acid ester, dimethyltoluate, dimethylmethane-bis-1-chloromethyl-2-methacryloyloxyethyl-4-cyclohexylcarbamic acid ester, 2' -bis (, 2,2 '-bis (4-methacryloxypropoxyphenyl) propane, 2' -bis (4-acryloxypropoxyphenyl) propane, 2 '-bis (4-methacryloxydiethoxyphenyl) propane, 2' -bis (4-acryloxydiethoxyphenyl) propane, 2 '-bis [3 (4-phenoxy) -2-hydroxypropane-1-methacrylate ] propane and 2,2' -bis [3 (4-phenoxy) -2-hydroxypropane-1-acrylate ] propane.

In addition to the (meth) acrylates listed above, the polymerizable dental composition may also include urethane (meth) acrylates, epoxy (meth) acrylates, and polyol (meth) acrylates.

Other suitable examples of compounds having a polymerizable double bond are isopropenyloxazoline, vinyl azalide, vinyl pyrrolidone, styrene and divinylbenzene.

Preferably, the amount of the polymerizable compound(s) of formula (I) and the additional compound(s) having a polymerizable double bond is from 5 to 80% by weight, more preferably from 10 to 60% by weight, relative to the total polymerizable dental composition.

Co-initiators

The polymerizable dental composition according to the present invention may further comprise one or more coinitiators for improving the photopolymerization efficiency of the photosensitizer (b).

Preferably, the polymerizable dental composition according to the invention comprises a co-initiator in the form of an amine. The dental composition may include one or more amine co-initiators.

The amine coinitiator is not particularly limited as long as it is capable of donating electrons in a photochemical process, for example, by means of a lone electron pair.

Preferably, the amine co-initiator is a tertiary amine selected from the group consisting of: trialkanolamine, 4-N, N-dialkylaminobenzonitrile, alkyl N, N-dialkylaminobenzoate, N-dialkylaminoethyl alkylacrylate and isoprene 4-N, N-dialkylaminobenzoateEsters, N-dialkylanilines, N-dialkyltoluidines, N-dialkanolylmethylamines, dialkylaminobenzethers, 1-or 2-dialkylaminonaphthalenes. Specifically, the tertiary amine is selected from the group consisting of: triethanolamine, alkyl 4-N, N-dialkylaminobenzoate, ethyl 4-N, N-dialkylaminobenzoate, 4-N, N-dialkylaminoethyl methacrylate, isoamyl 4-N, N-dialkylaminobenzoate, and 4,4' -N, N-bis (dialkylamino) benzophenone. In these amine compounds, the alkyl group may represent a linear, branched or cyclic alkyl group. Furthermore, in amine compounds in which more than one alkyl group is present, the alkyl groups may be the same or different, preferably the same. Preferably, the alkyl group is C_1-6Alkyl, more preferably C_1-4An alkyl group. Most preferably, the alkyl group is a methyl or ethyl group.

Particularly preferred amine coinitiators are tertiary amines selected from the group consisting of: triethanolamine, 4-N, N-dimethylaminobenzonitrile, methyl N, N-dimethylaminobenzoate, ethyl N, N-Dimethylaminobenzoate (DMABE), N-dimethylaminoethyl methacrylate and isoamyl 4-N, N-dimethylaminobenzoate, N-dimethylaniline, N-dimethyltoluidine, N-diethanolylmethylamine, dimethylaminobenzoic ether, 1-or 2-dimethylaminonaphthalene. More preferred amine co-initiators are tertiary amines selected from the group consisting of: triethanolamine, methyl 4-N, N-dimethylaminobenzoate, ethyl 4-N, N-Dimethylaminobenzoate (DMABE), 4-N, N-dimethylaminoethyl methacrylate, isoamyl 4-N, N-dimethylaminobenzoate, and 4,4' -N, N-bis (dimethylamino) benzophenone the most preferred amine co-initiator is ethyl 4-N, N-Dimethylaminobenzoate (DMABE).

Furthermore, the polymerizable dental composition according to the present invention may alternatively or additionally comprise a co-initiator in addition to the above-mentioned amine co-initiators.

For example, the co-initiator may also be selected from the group consisting of: amides, ethers, thioethers, ureas, thioureas, ferrocenes, sulfinic acids and salts thereof, salts of ferrocyanide, ascorbic acid and salts thereof, dithiocarbamic acid and salts thereof, salts of xanthates, salts of ethylenediaminetetraacetic acid, salts of tetraphenylboronic acid, silanes, and germanes.

From the abovementioned groups of coinitiators, other than amines, preference is given to silanes and germanes, in particular three hydrocarbon radicals each having R as for the compounds of the formula (VIII)¹⁵、R¹⁶And R¹⁷Trihydrocarbylsilanes or trihydrocarbylgermanes of the same meaning as defined. Of these, triphenylsilicon hydride (Ph) is preferable₃SiH) or triphenylgermanium hydride (Ph)₃GeH), and most preferably triphenylgermanium hydride (Ph)₃GeH)。

Furthermore, if the (b) sensitizer is an acylsilane or acylgermanium compound of formula (VIII), the co-initiator may be a sensitizer other than a compound of formula (VIII), such as the diketone and phosphine oxide photoinitiators described above. Such co-initiators may be added, for example, to improve the matching of the dental LED emission spectrum to the absorption of the photoinitiating system. For example, if the compound of formula (VIII) does not absorb or does not absorb sufficiently light in the range of 450 to 500nm, it is preferable to add a sensitizer having good absorption in this range. Preferably, the co-initiator which is a sensitizer other than a compound of formula (VIII) is a1, 2 or 1,3 diketone, more preferably a1, 2 diketone, most preferably camphorquinone.

Other Components

Optionally, the dental compositions of the present invention may include other components such as stabilizers, solvents, and/or particulate fillers.

The dental composition may include one or more stabilizers.

The term "stabilizer" as used herein means any compound capable of preventing spontaneous polymerization of the polymerizable compounds contained in the dental composition during storage. However, the stabilizer does not interfere with or prevent the intended polymerization cure of the dental composition during application.

Two groups of stabilizers are known, namely aerobic and anaerobic stabilizers.

Anaerobic stabilizers are stable free radicals, for example 2,2,6, 6-tetramethyl-1-piperidinyloxy (TEMPO), nitone or alkoxyamine radicals, phenothiazine or galvanoxyl radicals.

The aerobic stabilizing agent may be selected from the group consisting of: hydroquinone, hydroquinone monoalkyl ether, tert-butyl-hydroquinone, tert-butyl hydroxyanisole, propyl gallate and 2, 6-di-tert-butyl-p-cresol. Of these conventional stabilizers, 2, 6-di-t-butyl-p-cresol is preferred.

Preferably, the stabilizer is an aerobic stabilizer, more preferably a compound of formula (XI) and/or (XII):

wherein

R²²May be the same or different and independently represent a branched chain C_3-8Alkyl or alkenyl or C_3-8A cycloalkyl group or a cycloalkenyl group,

R²³is represented by C_1-6Alkyl or C_2-6Alkenyl, or C_1-6Fluoroalkyl or C_2-6A group consisting of a fluoroalkenyl group,

x represents C_1-8Alkyl or C_3-8A radical of a cycloalkyl group, and

n is 0,1 or 2.

It has surprisingly been found that the stabilizer classes of formula (XI) and/or (XII) provide a complete avoidance or at least a significant avoidance of discoloration upon storage and/or during photocuring. In particular, this class of stabilizers provides unexpected stabilization in acidic aqueous mixtures, such that dental compositions having a pH of less than 7 can be provided that do not or substantially do not discolor upon storage due to improved resistance to premature polymerization, and have excellent storage stability.

More preferably, the stabilizerIs a compound of formula (XI) and/or (XII), wherein R²²May be the same or different and independently represent a branched chain C_3-8Alkyl or C_3-8Cycloalkyl radical, and R²³Is represented by C_1-6Alkyl or C_1-6Fluoroalkyl, and n is 0 or 1. Even more preferably, the stabilizer is a compound of formula (XI) and/or (XII), wherein R²²May be the same or different and independently represent a branched chain C_3-8Alkyl, and R²³Is represented by C_1-6Alkyl, and n is 0. Most preferably, the stabilizer is a compound of formula (XIa), (XIb) or (XIIa):

wherein R is^o、R^oo、R^ooo、R^Δ、R^ΔΔAnd R^ΔΔΔMay be the same or different and independently represent an alkyl group or an ethyl group. It is particularly preferred that the stabilizer of formula (XIa), (XIb) or (XIIa) is a compound of the formula:

preferred is DTBHQ.

The stabilizer DTBHQ is particularly preferred because from experimental tests this stabilizer provides the best results in view of the problematic discoloration, i.e. there is no or almost no discoloration of the dental composition when stored at 50 ℃ for 30 days.

The discoloration upon storage and/or during photocuring can be determined according to ISO 7491:2000 (en).

The dental composition according to the present invention contains a stabilizer in an amount of 0.001 to 1% by weight, preferably 0.005 to 0.8% by weight, based on the total weight of the composition. When the amount of the stabilizer is less than the lower limit value of 0.001 indicated above, then the storage stability of the dental composition may be insufficient because the amount of the stabilizer is too small to provide a stabilizing effect. However, when the amount of stabilizer is above the maximum threshold of 1 wt%, then the applicability of the dental composition may be adversely affected, since higher amounts of stabilizer may interfere with or even significantly hinder the intended polymerization curing of the dental composition during application.

In addition, the polymerizable dental composition according to the present invention may comprise a suitable solvent. These solvents may be selected from water; alcohols, such as methanol, ethanol, propanol (n-, iso-), butanol (n-, iso-, tert-); ketones such as acetone and the like.

The dental composition of the present invention may preferably include 5 to 75% by weight of a solvent, based on the total weight of the composition.

Furthermore, the polymerizable dental composition according to the invention may comprise suitable particulate fillers. These particulate fillers may be selected from fillers currently used in dental compositions. The filler should be finely divided and preferably have a maximum particle diameter of less than about 10 μm and an average particle diameter of less than about 1 μm. The filler may have a monomodal or multimodal (e.g. bimodal) particle size distribution.

The filler may be an inorganic material. The filler may also be a crosslinked organic material that is insoluble in the polymerizable resin and optionally filled with an inorganic filler. The filler may be radiopaque. Examples of suitable inorganic particulate fillers are naturally occurring or synthetic materials, such as quartz; nitrides, such as silicon nitride; glasses derived from, for example, Ce, Sb, Sn, Zr, Sr, Ba, and Al; colloidal silicon dioxide; feldspar; borosilicate glass; kaolin; talc; titanium dioxide and zinc glass; and submicron silica particles, such as fumed silica. Examples of suitable non-reactive organic filler particles include filled or unfilled powdered polycarbonate or polyepoxide. Preferably, the surface of the filler particles is treated with a coupling agent to enhance the bond between the filler and the matrix. The use of suitable coupling agents includes gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane and the like.

The particulate filler may also be a filler obtainable by a process for preparing composite filler particles, the process comprising:

(a) coating a particulate filler having a median particle size (D50) of 1 to 1200nm with a coating composition comprising a film-forming agent, the film-forming agent forming a coating on the surface of the particulate filler, the coating exhibiting reactive groups on the surface of the coating, the reactive groups being selected from addition-polymerizable groups and step-growth-polymerizable groups, thereby forming a coated particulate filler; subsequently or simultaneously

(b) Agglomerating the coated particulate filler, optionally in the presence of another cross-linking agent and optionally in the presence of another particulate filler not displaying reactive groups, for providing a granulation of the coated particulate filler, wherein the granulation contains coated particulate filler particles and optionally further particulate filler particles separated and connected to each other by at least one coating layer, whereby the at least one coating layer may be cross-linked by cross-linking groups obtained by reacting reactive groups with the optional another cross-linking agent;

(c) optionally grinding, classifying and/or screening the granulation of the coated particulate filler; and

(d) optionally further cross-linking the granulation of the coated particulate filler;

for providing composite filler particles having a median particle size (D50) of 1 to 70 μm, wherein the reactive groups are converted into cross-linking groups obtained by reacting the reactive groups with optionally another cross-linking agent, and wherein the particulate filler is the major component by volume of the composite filler particle, as further described in EP-a 2604247.

The dental composition of the present invention may preferably comprise from 0.1 to 85% by weight of particulate filler, based on the total weight of the composition.

The dental compositions of the present invention may further contain preservatives, pigments, free radical scavengers, reactive and non-reactive diluents, coupling agents to enhance the reactivity of the fillers, rheology modifiers and surfactants.

Suitable preservatives may be selected from reducing agents such as vitamin C, inorganic sulphides, polysulphides and the like.

PREFERRED EMBODIMENTS

According to a preferred embodiment, the polymerizable dental composition according to the invention comprises:

(a) polymerizable compounds of the following formula (I):

X'-L-X"

(I)

wherein

X' represents a group of the following formula (II) or (III):

wherein

Dotted line represents

A double or triple bond, preferably a double bond, wherein in the case of a triple bond, no R is present⁴And R⁵；

The jagged lines indicate that formulas (II) and (III) encompass any of the (E) or (Z) isomers,

z' and Z ", which may be the same or different, independently represent an oxygen atom or > N-R, wherein

R is hydrogen atom or straight chain C_1-4Alkyl or C_2-4Alkenyl, or branched or cyclic C_3-6Alkyl or alkenyl, which may be substituted by acidic groups, preferably by phosphate monoester groups (-O-P (═ O) (OH)₂) Or a group of the following formula (IV):

wherein

The jagged lines indicate that formula (IV) includes any of the (E) or (Z) isomers,

preferably R is a group of formula (IV),

R¹¹represents a hydrogen atom or a straight chain C_1-4Alkyl or C_2-4Alkenyl or branched or cyclic C_3-6Alkyl or alkenyl, preferably representing a hydrogen atom or a linear C_1-4Or branched C_3-6Alkyl radical, and

R¹²represents a hydrogen atom;

R¹³and R¹⁴，

May be the same or different and independently represent a hydrogen atom or a linear C_1-4Alkyl or C_2-4Alkenyl or branched or cyclic C_3-6Alkyl or alkenyl, preferably representing a hydrogen atom or a linear C_1-4Or branched C_3-6Alkyl, or R¹³And R¹⁴Together represent an oxygen atom which together with the adjacent carbon atoms forms a carbonyl group;

R¹represents a hydrogen atom;

R²represents a hydrogen atom; or straight chain C_1-4Or branched C_3-6Alkyl, said group may be substituted by at least one member selected from the group consisting of hydroxy, C_1-6Partially substituted by alkoxy and acidic groups, preferably by C_1-6Alkoxy substitution;

R³represents a hydrogen atom or a straight chain C_1-4Alkyl or C_2-4Alkenyl or branched or cyclic C_3-6Alkyl or alkenyl, preferably representing a hydrogen atom or a linear C_1-4Or branched C_3-6An alkyl group;

R⁴and R⁵，

May be the same or different and independently represent a hydrogen atom or a linear C_1-4Or branched C_3-6Alkyl, preferably R⁴And R⁵Each represents a hydrogen atom;

R⁶represents a hydrogen atom or a straight chain C_1-4Alkyl or C_2-4Alkenyl or branched or cyclic C_3-6Alkyl or alkenyl, preferably representing a straight chain C_1-4Or branched or cyclic C_3-6Alkyl, said group may be substituted by C_1-6Alkoxy substitution;

x' represents a moiety of the following formula (V) or (VI):

wherein

The jagged lines indicate that formula (V) encompasses any of the (E) or (Z) isomers,

z and Z, which may be the same or different, independently represent an oxygen atom or > N-R', wherein

R 'has the same meaning as defined above for R, preferably R' is a group (IV);

R⁷is a hydrogen atom, and is a hydrogen atom,

R⁸represents a hydrogen atom; or straight chain C_1-4Or branched C_3-6An alkyl group, said group being optionally substituted by at least one member selected from the group consisting of hydroxyl, thiol, C_1-6Partially substituted by alkoxy and acidic groups, preferably by C_1-6Alkoxy substitution;

R⁹represents a hydrogen atom or a straight chain C_1-4Alkyl or C_2-4Alkenyl or branched or cyclic C_3-6Alkyl or alkenyl, preferably representing a hydrogen atom or a linear C_1-4Or branched C_3-6An alkyl group;

R¹⁰represents a hydrogen atom or a straight chain C_1-4Alkyl or C_2-4Alkenyl or branched or cyclic C_3-6Alkyl or alkenyl, preferably representing a hydrogen atom or a linear C_1-4Or branched C_3-6An alkyl group;

wherein R is⁴And R, and/or R¹¹And R¹³May together represent an alkylene or alkenylene group which together with the bridging atom to which it is attached forms a 3-to 6-membered saturated or unsaturated ring;

wherein R is⁹And R' and/or R¹¹And R¹³May together represent an alkylene or alkenylene group which together with the bridging atom to which it is attached forms a 3-to 6-membered saturated or unsaturated ring; and is

Wherein R is³And R⁹May represent an alkylene or alkenylene group which together with the bridging atom to which it is attached forms a 4-to 6-membered unsaturated ring; and is

L may be present or absent and, when present, represents a divalent linking group of formula (VII)

Wherein m is 0, n is 0 or 1, and o is 0 or 1, and p is 1, and when L is absent, X' and X "are directly bonded by a single bond; preferably, L is a single bond;

wherein if X 'represents a group of formula (II), then X' is a group of formula (V), and if X 'represents a group of formula (III), then X' is a group of formula (VI);

(b) a photosensitizer, and

(c) and (4) an iodine salt.

According to a particularly preferred embodiment, the polymerizable dental composition according to the invention comprises:

(a) polymerizable compounds of the following formula (I):

X'-L-X"

(I)

wherein

X' represents a group of the following formula (II) or (III):

wherein

The dotted line represents a double bond;

the jagged lines indicate that formulas (II) and (III) encompass any of the (E) or (Z) isomers,

z' and Z ", which may be the same or different, independently represent > N-R, wherein

R is hydrogen atom or straight chain C_1-4Alkyl or C_2-4Alkenyl, or branched or cyclic C_3-6Alkyl or alkenyl, which may be substituted by acidic groups, preferably by phosphate monoester groups (-O-P (═ O) (OH)₂) The substitution is carried out by the following steps,

R¹represents a hydrogen atom, and is represented by,

R²represents a hydrogen atom; or straight chain C_1-4Or branched C_3-6Alkyl, said group may be substituted by C_1-6Alkoxy substitution;

R³represents a hydrogen atom or a straight chain C_1-4Or branched C_3-6An alkyl group;

R⁴and R⁵Each represents a hydrogen atom;

R⁶represents a straight chain C_1-4Or branched or cyclic C_3-6Alkyl, said group may be substituted by C_1-6Alkoxy substitution;

x' represents a moiety of the following formula (V) or (VI):

wherein

The jagged lines indicate that formula (V) encompasses any of the (E) or (Z) isomers,

z and Z, which may be the same or different, independently represent an oxygen atom or > N-R', wherein

R' has the same meaning as defined above for R;

R⁷is a hydrogen atom, and is a hydrogen atom,

R⁸

represents a hydrogen atom or a straight chain C_1-4Or branched C_3-6Alkyl, said radical being optionally substituted by C_1-6Alkoxy substitution;

R⁹represents a hydrogen atom or a straight chain C_1-4Or branched C_3-6An alkyl group;

R¹⁰represents a hydrogen atom or a straight chain C_1-4An alkyl group;

or alternatively, the one or more of,

radicals R and R⁴And/or residues R' and R⁵Preference is given to the residues R and R⁴And residues R' and R⁵May together represent an alkylene or alkenylene group which together with the bridging atom to which it is attached forms a 4-to 6-membered saturated or unsaturated ring;

residue R³And R⁹Or a residue R⁴And R⁹May together represent a single bond, alkylene or alkenylene group which together with the bridging atom to which they are attached form a 4-to 6-membered unsaturated ring;

residue R¹¹Can be reacted with a residue R¹³Or R¹⁴Together represent a single bond or an alkylene or alkenylene group which together with the bridging atom to which they are attached form a 3-to 6-membered unsaturated ring having one or two carbon-carbon double bonds; and

l is a single bond;

wherein if X 'represents a group of formula (II), then X' is a group of formula (V), and if X 'represents a group of formula (III), then X' is a group of formula (VI);

(b) a photosensitizer, and

(c) and (4) an iodine salt.

The polymerizable compound of formula (I) as defined in claim 1 can be used for the preparation of a dental composition, preferably a dental composition according to the present invention as described above.

The invention will now be further illustrated by the following examples.

Examples of the invention

Preparation examples

Compounds of formula (I) according to the invention having the following structural formula have been tested:

scheme 8 chemical Structure of Compounds of formula (I) tested

In addition, for comparison, compounds not according to the present invention having the following structural formula have been tested:

scheme 9 chemical Structure of polymerizable Compounds tested for comparison

General procedure for the synthesis of compounds of formulae (Ib) and (Ic) and comparative compounds (C1), (C2) and (C3):

A) synthesis of N, N' -dialkyl-1, 4-butene:

potassium carbonate (2.5 equivalents) was added to the alkylamine (15 equivalents) and cooled to 0 to 5 ℃. The corresponding dibromide (1 equivalent) was added in portions and the resulting mixture was stirred at room temperature for 3 to 5 hours. Next, the remaining amine was removed by distillation, and the resulting residue was suspended in acetone. After filtration of the salt, the acetone was evaporated.

B) Synthesis of N, N' -dialkyl-1, 4-butane:

the corresponding alkyl chloride (2.1 equivalents) was added dropwise to a solution of 1, 4-diaminobutane (1 equivalent)/methanol at 50 ℃. The resulting mixture was stirred at 60 ℃ for 24 hours. Next, the methanol was removed by distillation, and the residue was diluted with 2m naoh and extracted with DCM. The organic layer was dried (Na)₂SO₄) And the solvent is evaporated.

Acrylation of N, N '-dialkyl-1, 4-butene and N, N' -dialkyl-1, 4-butane:

the resulting crude diamine was dissolved in THF and triethylamine (3.5 equivalents) was added. Acryloyl chloride (2.2 equivalents) was added dropwise at 0 to 5 ℃, after which the resulting mixture was stirred at room temperature for 2.5 hours. Next, THF was evaporated, ethyl acetate was added, and the resulting mixture was washed 3 times with 2N HCl and once with water. The organic layer was dried (Na)₂SO₄) The solvent was evaporated and the residue was purified by flash chromatography (eluent: ethyl acetate).

N, N '-bisacryloyl-N, N' -bisallyl-2, 4-pent-2-enediamine (Ib)

14% of yield, η_23℃＝409±0Pa*s；n_D ²⁰＝1.526

¹H NMR(CDCl₃):δ(ppm)＝6.50-6.26(m,5H,2xH ₂CCHC(O)),5.84-5.70(m,2H,H₂CCHCH₂),5.68-5.60(m,2H,H₂CCHC(O)),5.61-5.51(m,2H,H₂CHCCHCH₂),5.31(m,1H,HC(CH₃)HCCHCH₂),5.25-5.08(m,4H,H ₂CCHCH₂),4.06-3.71(m,6H,HC(CH₃)HCCHCH ₂,2xH₂CCHCH ₂)；

¹³C NMR(CDCl₃):δ(ppm)＝166.4,166.3,166.1(C(O)CHCH₂),135.1-132.8(H₂CCHCH₂),128.5-126.5(H₂ CCHC(O),HC(CH₃)HCCHCH₂),117.5-116.4(H₂ CCHCH₂),50.0(HC(CH₃)HCCHCH₂),49.1-45.5(H₂CCHCH₂,H₂ CHCCHCH₂),18.7,17.1,16.8(HC(CH₃)HCCHCH₂)；

FT-IR：[cm^-1]＝3532,3491,3080,2977,2924,1644,1609,1416,1362,13281276,1217,1184,1129,1059,976,919,794。

N, N '-bisacryloyl-N, N' -bisallyl-1, 4-but-2-enediamine (Ic)

33% of yield, η_23℃＝428±3Pa*s；n_D ²⁰＝1.5095

¹H NMR(CDCl₃):δ(ppm)＝6.54-6.47(m,2H,H ₂CCHC(O)),6.33-6.25(m,2H,H ₂CCHC(O)),5.66-5.58(m,2H,H₂CCHC(O)),5.56-5.51(m,2H,H₂CHCCHCH₂),3.99-3.89(m,4H, ₂HCHCCHCH ₂),3.30-3.18(m,H₃CCH₂CH ₂) 1.54 ('quintet', J ═ 7.0,4H, H₃CCH ₂CH₂),0.85(t,J＝7.3,6H,H ₃CCH₂CH₂)；

¹³C NMR(CDCl₃):δ(ppm)＝166.1,165.9(C(O)CHCH₂),128.1-127.3(H₂ CCHC(O),H₂CHCCHCH₂),117.5-116.7(H₂ CCHCH₂),49.1-47.4(H₃CCH₂ CH₂,H₂ CHCCHCH₂),22.5-20.9(H₂CH₂ CCH₂CH₂,H₃CCH₂CH₂),11.2-11.0(H₃ CCH₂CH₂)；

FT-IR：[cm^-1]＝3525,2963,2932,2875,1645,1609,1442,1426,1368,1279,1224,1123,1059,975,888,794。

Comparative example

N, N '-diacetyl-N, N' -bisallyl-1, 4-but-2-enediamine (C1)

Yield: 24 percent; t is_m＝32℃；n_D ²⁰＝1.505

¹H NMR(CDCl₃):δ(ppm)＝5.69-5.61(m,2H,H₂CCHCH₂),5.43(m,2H,H₂CHCCHCH₂),5.12-4.98(m,4H,H ₂CCHCH₂)3.88-3.74(m,8H, ₂HCHCCHCH ₂,H₂CCHCH ₂),2.00(s,6H,C(O)CH ₃)

¹³C NMR(CDCl₃):δ(ppm)＝170.3-169.4(C(O)CH₃),132.9-132.3(H₂CCHCH₂),127.9-127.0(H₂CHCCHCH₂),116.7-116.2(H₂ CCHCH₂),49.9-46.2(H₂CCHCH₂,H ₂CHCCHCH₂)21.1-21.0(C(O)CH₃)；

FT-IR：[cm^-1]＝3074,3012,2986,2916,1633,1468,1411,1360,1242,1187,1035,978,919。

N, N '-bisacryloyl-N, N' -bisallyl-1, 4-butanediamine (C2)

35% of yield, η_23℃＝382±1Pa*s；n_D ²⁰＝1.515

¹H NMR(CDCl₃):δ(ppm)＝6.58-6.28(m,4H,H ₂CCHC(O)),5.80-5.71(m,2H,H₂CCHCH₂),5.68-5.60(m,2H,H₂CCHC(O)),5.21-5.10(m,4H,H ₂CCHCH₂),4.02-3.93(m,4H,H₂CCHCH ₂),3.41-3.40(m,4H,H ₂CH₂CCH₂CH ₂),1.55(m,4H,H₂CH ₂CCH ₂CH₂)；

¹³C NMR(CDCl₃):δ(ppm)＝166.6,166.0(C(O)CHCH₂),133.3,133.0(H₂CCHCH₂),128.2-127.5(H₂ CCHC(O)),117.1-116.7(H₂ CCHCH₂),50.1-48.6(H₂CCHCH₂),46.9-45.9(H₂ CH₂CCH₂ CH₂),26.5-25.0(H₂CH₂ CCH₂CH₂)；

FT-IR：[cm^-1]＝3472,3082,2924,1646,1609,1428,1374,1217,1163,1133,1059,978,957,918,794。

N, N '-bisacryloyl-N, N' -bisallyl-1, 4-butanediamine (C3)

26% of yield, η_23℃＝486±1Pa*s；n_D ²⁰＝1.515

¹H NMR(CDCl₃):δ(ppm)＝6.40-6.33(m,2H,H ₂CCHC(O)),6.16-6.09(m,2H,H ₂CCHC(O)),5.49-5.43(m,2H,H₂CCHC(O)),3.21-3.05(m,8H,H ₂CH₂CCH₂CH ₂,H₃CCH₂CH ₂),1.38(m,8H,H₃CCH ₂CH₂,H₂CH ₂CCH ₂CH₂),0.70(m,H₃CCH ₂CH₂)；

¹³C NMR(CDCl₃):δ(ppm)＝165.5,165.4(C(O)CHCH₂),127.5-126.9(H₂ CCHC(O)),49.1-45.3(H₃CCH₂ CH₂,H₂ CH₂CCH₂ CH₂),26.3-20.5(H₂CH₂ CCH₂CH₂,H₃CCH₂CH₂),10.9-10.6(H₃ CCH₂CH₂)；

FT-IR：[cm^-1]＝3314,2963,2933,2874,1645,1608,1481,1449,1426,1374,1263,1227,1166,1136,1058,978,954,794。

Differential Scanning Calorimetry (DSC) experiment

For DSC experiments, compositions containing a compound of formula (Ib), (Ic), (C1), (C2), or (C3), 0.22 to 0.35 mol% of a stabilizer, 0.3 wt% Camphorquinone (CQ) as a sensitizer, and 0.4 wt% ethyl 4- (dimethylamino) benzoate (DMABE) as a co-initiator are provided. In these compositions, mol% is indicated based on the molar amount of the compound of formula (Ib), (Ic), (C1), (C2) or (C3) and wt% is indicated based on the total weight of the composition, wherein the remaining mass/weight of the composition consists of the compound of formula (Ib), (Ic), (C1), (C2) or (C3). Curing light at 37 ℃ with SmartLite Focus LED from Dentsply at 100mW/cm²The composition was irradiated and DSC was performed with the apparatus Perkin Elmer DSC 7/DPA 7.

As a result:

the DSC measurements listed in table 1 and depicted in fig. 2 show the formulae (Ia), (Ib) and (I) according to the inventionc) The compounds have an advantageous enthalpy of polymerization, which is comparable to the enthalpy of polymerization of (meth) acrylates customarily used in dental compositions, typically of the order of Δ_RH is-80 to-120 kJ/mol. Furthermore, as can be gathered from tables 1 and 2 below, the compounds of formulae (Ia), (Ib) and (Ic) have advantageous viscosity, color, odor, solubility and refractive index for the preparation of polymerizable dental compositions. The parameters Refractive Index (RI) and viscosity are depicted in fig. 1.

Table 1: experimental results for Compounds of formulae (Ia), (Ib) and (Ic)

^*)Determination at 37 ℃

^**)"-" means no solubility

^***)"+ +" means excellent solubility

In addition to the characteristics listed in Table 1, for compounds (Ia), (Ib) and (Ic) the parameter maximum polymerization rate (Rp) was determined_max) Maximum heat flow time (t)_max) (see compounds (Ib) and (Ic) of fig. 3)), flexural strength and E modulus (see compounds (Ib) and (Ic) of fig. 4), which are listed in the following table 2:

DSC measurements obtained for comparative compounds (C1), (C2), and (C3) are listed in table 3 below. The results show that the comparative compound (C2) can have an advantageous polymerization enthalpy, which is comparable to the polymerization enthalpy of (meth) acrylates commonly used in dental compositions, while the polymerization enthalpy of the comparative compound (C3) is used to provide a polymerization enthalpy comparable to that of conventional (meth) acrylatesThe compatibility of the alkenoic acid ester is outside the desired value range of-80 to-120 kJ/mol. For the comparative compound (C1), the enthalpy of polymerization was not determined, since this compound failed in the pretest used to determine E modulus and flexural strength. Furthermore, as can be gathered from table 4 below, the comparative compounds (C2) and (C3) have a significantly lower maximum polymerization rate (Rp) compared to the compounds of formulae (Ia), (Ib) and (Ic) according to the invention_max). In addition, the maximum heat flow times (t) of compounds (C2) and (C3) were compared_max) T compared to the compounds of formulae (Ia), (Ib) and (Ic) according to the invention_maxIs significantly higher. In addition, the E modulus of the cured dental composition based on comparative compound (C2) was significantly lower compared to the cured dental composition according to the invention based on compounds (Ia), (Ib) and (Ic). Furthermore, the comparative compound (C2) has the following drawbacks: it is insoluble in alcohols such as ethanol or isopropanol, but only in the tested solvents acetone and methacrylic acid.

Details of the characteristics obtained for comparative compounds (C1), (C2), and (C3) can be collected from tables 3 and 4 below.

Table 3: experimental results for comparative compounds of formulae (C1), (C2), and (C3).

^#)"n.d." means "not determined"

^*)Determination at 37 ℃

^**)"-" means no solubility

^***)"+ +" means excellent solubility

In addition to the properties listed in Table 3, the parameter maximum polymerization rate (Rp) was determined for liquid comparison compounds of formulae (C2) and (C3)_max) Maximum heat flow time (t)_max)(t_max) (see fig. 3), flexural strength and E modulus (see fig. 4), which are listed in table 4 below:

the IR spectra of the compound of formula (Ib) depicted in fig. 5 and the comparative compound (C2) depicted in fig. 7 show that in the upper spectrum recorded before polymerization, v ═ 1.500-1800cm were present^-1Two bands within range: at about 1.650cm^-1Lower and at about 1.610cm^-1The following steps. After polymerization, as can be collected from the lower spectra of fig. 5 and 7, one band is 1.500-1800cm at v^-1Within range, and the three bands remain as follows: at about 1.660cm^-1At about 1.620cm, below (C ═ O)^-1Lower (allyl C ═ C) and at about 1.600 lower (acryloyl C ═ C). About 1.650cm^-1The band of (a) is represented by amide I band (C ═ O), and about 1.610 band is amide II (N — H). Without wishing to be bound by theory, it is believed that the amide I and II bonds indicate the formation of a cyclopolymerization, i.e., the formation of a δ -lactam ring as described above in connection with scheme 1.

In summary, the above experimental examples support that the polymerizable compounds of formula (I) of the present invention have a polymerization enthalpy that makes possible the polymerization of said compounds together with the conventional (meth) acrylates, (meth) acrylamides and allyl ethers commonly used in dental compositions. In addition, the compounds of formula (I) have advantageous viscosity, color, odor, solubility and refractive index, making them particularly useful for preparing polymerizable dental compositions.

Example 1

■ M-BAABE (bis-N, N-Methyl radicalAcryloyl-, batch number: MS1261), yield: 29 percent

¹H NMR(CDCl₃):δ(ppm)＝5.79-5.68(m,2H,H₂CCHCH₂),5.59-5.46(m,2H,H₂CHCCHCH₂),5.23-5.09(m,4H,H ₂CCHCH₂),5.14(s,2H,H₂CC(CH ₃)C(O))5.04(s,2H,H₂CC(CH ₃)C(O)),4.00-3.89(m,8H, ₂HCHCCHCH ₂,H₂CCHCH ₂)；1.95(s,6H,2x Me)

¹³C NMR(CDCl₃):δ(ppm)＝162.5(C(O)C(CH₃)CH₂),140.6(2x H₂CCHCH₂),133.5-132.6(H₂ CC(CH₃)C(O)),128.7-128.1(H₂CHCCHCH₂),117.7-116.2(H₂ CCHCH₂),50.5-48.6(H₂CCHCH₂),46.7-45.2(H ₂CHCCHCH₂),20.6(Me)

■Me2DPI

Formulations

Adhesive formulations 1 and 2 were prepared by mixing the individual components as shown in table 5.

Table 5: composition of adhesive formulation

Formulation numbering		Application example 1	Application example 2
				Adhesive agent		1	2
M-BAABE	By weight%	36.6	44.6
				MDP	By weight%	12.2	11.0
2-propanol	By weight%	16.0	15.0
				Water (W)	By weight%	20.2	19.1
Camphorquinone	By weight%	1.6	1.6
				Dimethylaminobenzonitrile	By weight%	0.7	0.7
Me2DPI	By weight%	0.8	0.8
				Other resin components, stabilizers	By weight%	11.9	7.2
Total of	By weight%	100.0	100.0

Abbreviations	Name of substance	CAS number
			M-BAABE	N, N' - (2E) -but-2-ene-1, 4-diallylbis- [ (N-isobutan-2-ene-1) amide]	-
MDP	2-methyl-, 10- (phosphonooxy) decyl 2-propenoic acid	85590-00-7
			Me2DPI	Bis (4-methylphenyl) iodohexafluorophosphate	60565-88-0

Preparation of

In a closed container and under yellow light conditions, the liquids were mixed in the ratios given in table 1 and stirred for 2 hours at 22 ℃.

Applications of

All solutions were applied on pre-conditioned rough surfaces (enamel and dentin) of human molars in a self-etching (no pre-etch) and etch and rinse mode (with phosphoric acid for pre-etch) using the following steps: spread out using an applicator hairbrush, gently agitate for 20 seconds, allow solvent to evaporate through for at least 5 seconds, and finally blue cure for 10 seconds (minimum output level 800mW/cm 2). The spectral TPH3(a2) post-composite was positioned onto the respective surface and blue-cured for use according to its instructions. Samples were stored in water at 37 ℃ for 24 hours, and then the shear binding strength was determined using a Zwick tester (table 4). The arithmetic mean and standard deviation were calculated from six samples of each composition and separately on each template (enamel/dentin).

		Application example 1	Application example 2
				Adhesive agent		1	2
Shear bond strength on form
				Enamel, self-etching mode	MPa	11.3±1.5	10.3±0.9
Dentin, self-etching mode	MPa	16.9±1.4
				Enamel, etch and rinse modes	MPa	22.1±2.0	15.0±1.4
Dentine, etch and rinse modes	MPa	23.3±2.8	19.3±4.4
				pH value	-	2.4	2.5

■ ternary camphorquinone/amine/iodine salt (BAABE, Me2 DPI; application example 1) initiator System vs. binary camphorquinone/amine initiator System (comparative example 1)

Formulations

Adhesive formulations 1 and 2 were prepared by mixing the individual components as shown in table 6.

Table 6: composition of adhesive formulation

Formulation numbering		Application example 3	Comparative example 1
				Adhesive agent		3	4
BAABE	By weight%	40.6	40.9
				MDP	By weight%	11.6	11.7
2-propanol	By weight%	15.5	15.7
				Water (W)	By weight%	19.6	19.6
Camphorquinone	By weight%	1.6	1.6
				Dimethylaminobenzonitrile	By weight%	0.7	0.7
Me2DPI	By weight%	0.8	0.0
				Other resin components, stabilizers	By weight%	9.6	9.8
Total of	By weight%	100.00	100.00

Abbreviations	Name of substance	CAS number
			BAABE	N, N' - (2E) -but-2-ene-1, 4-diallylbis- [ (N-prop-2-ene-1) amide]	1620399-32-7
MDP	2-methyl-, 10- (phosphonooxy) decyl 2-propenoic acid	85590-00-7
			Me2DPI	Bis (4-methylphenyl) iodohexafluorophosphate	60565-88-0

		Application example 3	Comparative example 1
				Adhesive agent		3	4
Shear bond strength on form
				Enamel, self-etching mode	MPa	21.5±3.4	15.5±2.2
Dentin, self-etching mode	MPa	30.9±5.2	34.4±1.0
				pH value	-	2.5	2.5

Claims (15)

1. A polymerizable dental composition comprising

(a) Polymerizable compounds of the following formula (I):

X'-L-X"

(I)

wherein

X' represents a group of the following formula (II) or (III):

wherein

Dotted line represents

A double or triple bond, wherein in the presence of a triple bond, R is absent⁴And R⁵；

The jagged lines indicate that formulas (II) and (III) encompass any of the (E) or (Z) isomers,

z' and Z ", which may be the same or different, independently represent an oxygen atom, a sulfur atom or > N-R, wherein

R is a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group, or a group of formula (IV):

wherein

The jagged lines indicate that formula (IV) includes any of the (E) or (Z) isomers,

R¹¹and R¹²，

May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group;

R¹³and R¹⁴，

May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group; or R¹³And R¹⁴Together represent an oxygen atom which together with the adjacent carbon atoms forms a carbonyl group;

R¹and R²，

May be the same or different, independently represent a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted with at least one moiety selected from the group consisting of hydroxyl, alkoxy and acidic groups;

R³represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group;

R⁴and R⁵，

May be the same or different, independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted with an alkoxy or acidic group;

R⁶represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which groups can be substituted by alkoxy groups;

x "represents a moiety selected from the group consisting of a hydroxyl group, a thiol group, an alkoxy group and an acidic group, or a moiety of the following formula (V) or (VI):

wherein

The jagged lines indicate that formula (V) encompasses any of the (E) or (Z) isomers,

z and Z, which may be the same or different, independently represent an oxygen atom, a sulfur atom or > N-R', wherein

R' is a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted with an alkoxy or acidic group; or R' is independently a group of formula (IV) as defined for R;

R⁷and R⁸

May be the same or different, independently represent a hydrogen atom; a linear, branched or cyclic alkyl or alkenyl group, said group being capable of being substituted with at least one moiety selected from the group consisting of a hydroxyl group, a thiol group, an alkoxy group and an acidic group;

R⁹represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which group can be substituted by an alkoxy or acidic group;

R¹⁰represents a hydrogen atom; or a linear, branched or cyclic alkyl or alkenyl group, which groups can be substituted by alkoxy groups;

or alternatively, the one or more of,

R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰r' and, if present, R¹¹、R¹²、R¹³And R¹⁴Any two residues in (a) can together represent an alkylene or alkenylene group, which can be substituted byAlkoxy, acidic groups or-NR^▲R^▼Is substituted by radicals in which R^▲And R^▼Independently of one another, represents a hydrogen atom or an alkyl group; or

R¹、R²、R³、R⁴、R⁵、R⁶、R、R⁷、R⁸、R⁹、R¹⁰R' and, if present, R¹¹、R¹²、R¹³And R¹⁴Any two residues in (A) that are not geminal or vicinal groups are capable of representing a single bond together,

wherein the single bond or the optionally substituted alkylene or alkenylene together with the bridging atom to which the residue is attached form a 3-to 8-membered saturated or unsaturated ring,

wherein the polymerizable compound of formula (I) can include one or more of the 3-to 8-membered saturated or unsaturated rings; and is

L may be present or absent, represents a divalent linking group when present, and X' and X "are directly bonded by a single bond when absent;

(b) a photosensitizer, and

(c) and (4) an iodine salt.

2. The dental composition of claim 1 wherein R of R and/or R¹³And R¹⁴Together represent an oxygen atom which, together with an adjacent carbon atom, forms a carbonyl group.

3. The dental composition of claim 1 or 2, further comprising

(d) Coinitiators, preferably amine coinitiators.

4. The dental composition according to claim 1 or 2 wherein L is a group of formula (VII)

Wherein

m, n and o, which may be the same or different, are integers from 0 to 3; and p is 0,1 or 2.

5. The dental composition of claim 4 wherein p is 0.

6. The dental composition of claim 4 wherein p is 1.

7. The dental composition according to any one of claims 4 to 6 wherein n is 0.

8. The dental composition according to claim 6 or 7 wherein m or o is 0.

9. The dental composition of any of the preceding claims further comprising a stabilizer, a solvent, and/or a particulate filler.

10. Dental composition according to any of the preceding claims selected from dental adhesives, dental primers, dental resin modified glass ionomer cements, pit and fissure sealants, dental composites or dental flow agents.

11. The dental composition according to any of the preceding claims wherein the polymerizable compound of formula (I) has a refractive index in the range of from 1.500 to 1.580.

12. The dental composition according to any of the preceding claims, which is free of N, N' -diallyl-1, 4-bisacrylamido- (2E) -but-2-ene (BAABE).

13. The tooth of any preceding claimA composition for use in a subject, wherein the acidic groups are selected from the group consisting of carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, and phosphate monoester groups (-O-P (═ O) (OH)₂)。

14. Use of a polymerizable compound of formula (I) according to claim 1 for the preparation of a dental composition.

15. The use of claim 14, wherein the dental composition is a dental composition according to any one of claims 1 to 13.