DE202009016522U1 - Infiltrant for the treatment of an enamel lesion - Google Patents

Abstract

Infiltrant for the treatment of an enamel lesion consisting of
a) 30-99% of aromatic monomers,
b) 0-70% aliphatic monomers,
c) 0.05-5% initiators and
d) other dental additives, wherein
the infiltrant at room temperature (23 ° C) has a penetration coefficient PK according to Washburn equation greater than 50 cm / s and a refractive index n _D in the cured state between 1.53 and 1.65.

Description

The The invention relates to an infiltrant for the treatment of enamel lesions. The lesion is permanently sealed by the infiltrant and masked, d. H. optically to the surrounding (not defective) tooth enamel equalized.

lesions in enamel, especially in the anterior region (labial) an ugly or unhealthy appearance result. For example, orthodontic causes Braces often contain such lesions, in particular so-called "white spot lesions ".

lesions In enamel are mainly by demineralization caused. Such lesions can reach up to 2 mm in the enamel and have opposite healthy Enamel has increased porosity, causing it become visible, resulting in the aforementioned unsightly or unhealthy appearance of the teeth can. Furthermore, such lesions (untreated) to progressing caries to the dentin and finally Cavitation (complete destruction of tooth structure) to lead.

The published international application WO 07/131725 A1 , describes the infiltration of carious enamel lesions by light-curing resins with a penetration coefficient PK> 50 cm / s. The resins penetrate the increasingly porous areas and are subsequently cured or allowed to cure and thus prevent the progression of caries (caries progression). The infiltrant described there is particularly preferably intended to contain the composition 22.5% by weight of 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane [bis-GMA]; 67.5% by weight of triethylene glycol dimethacrylate. [TEGDMA]; 10 wt .-% ethanol, <1 wt .-% DABE, <1 wt .-% camphorquinone and a penetration coefficient PK = 129.3 cm / s have.

The described infiltration process can also improve the cosmetic appearance ( Paris S, Meyer-Lückel H: Masking of labial enamel White spot lesions by resin infiltration - A clinical report; Quintessence Int 2009, 40, 713-718 ).

The known infiltrants are still in need of improvement, so that an infiltrated lesion visually surrounds it Enamel is better aligned and at the same time long lasting remains sealed.

improvement also exists in terms of hardening properties of the infiltrant, in particular the depth of cure, the bond strength with the enamel, as well as the mechanical Properties of the cured infiltrant, in particular also the stress crack stability.

A disadvantage of the infiltrants of WO 2007/131725 A1 is also that they are substantially permeable to X-rays (translucent) and therefore are not or only very difficult to detect in an X-ray diagnosis by the dentist. This invalidates one of the most important tools for detecting the extent and location of existing infiltrations. Apart from that, it is difficult to determine if the infiltrants have insufficient X-ray opacity due to the insufficient radiopacity of the infiltrated lesions, because they can not be differentiated from the infiltrated area, or very poorly, under the infiltrated lesion. To determine a progressive caries, then elaborate exactly reproducible bite wing recordings are required, as in the German utility model DE 20 2008 006814 U1 are described.

the Known in the art, usually in dental materials Preparation of radiopacity filler particles Disadvantages, since particle-containing infiltrants infiltrate poorly and / or not sufficiently radiopaque and / or storage stable are, for example, by gradual agglomeration and / or sedimentation the particle.

• (a) 30–99 Gew-% aromatischen Monomeren und
• (b) bis zu 70 Gew.-% aliphatischen Monomeren,
• (c) 0,05–5 Gew.-% Initiatoren und
• (d) sonstigen dentalüblichen Additiven, wobei

der Infiltrant bei Raumtemperatur (23°C) einen Penetrationskoeffizienten PK gemäß Washburn-Gleichung größer 50 cm/s und eine Brechzahl n_D im ausgehärteten Zustand nach ISO 489:1999 zwischen 1,53 und 1,65 aufweist.The disadvantages of the known infiltrants are surprisingly, at least in part, overcome by an infiltrant for infiltration of porous enamel lesions consisting of

• (a) 30-99% by weight of aromatic monomers and
• (b) up to 70% by weight of aliphatic monomers,
• (c) 0.05-5% by weight of initiators and
• (D) other dental additives, wherein

the infiltrant at room temperature (23 ° C) a penetration coefficient PK according to Washburn equation greater than 50 cm / s and a refractive index n _D in the cured state after ISO 489: 1999 between 1.53 and 1.65 has.

Of the Infiltrant according to the invention offers a simple, fast, safe and gentle treatment option, which improves the appearance of defective teeth for a long time and prevent progressive caries, or at least long-lasting Delayed and the patient an elaborate and spares uncomfortable filling therapy.

First some terms used in the context of the invention are explained. The term infiltrant denotes a liquid to be hardened, deep into a natural enamel lesion (a porous solid) can penetrate. To By penetrating the lesion, the infiltrant can polymerize there become.

monomers are substances that consist of monomer molecules. monomer molecules are able to polymerize. Polymerization is every process in the monomer or a mixture of monomers to a polymer or copolymer (macromolecules) are reacted.

from Term monomers should also be used here as oligomers (prepolymers) which are capable of polymerizing.

aromatic Monomers contain at least one aromatic group. An aromatic Group denotes a planar, annular atomic group with conjugated double bonds.

monocyclic aromatic monomers contain only one (single) aromatic group per monomer molecule.

polycyclic aromatic monomers contain at least two aromatic groups (with common atoms or without common atoms) per monomer molecule.

aliphatic Monomers do not contain an aromatic group.

Cross-linking Monomers have two or more polymerizable groups and can therefore crosslinked polymers in a polymerization Form (macromolecules).

d

Abstand, um den sich die Monomerflüssigkeit bewegt

γ

Oberflächenspannung der Monomerflüssigkeit (gegen Luft)

θ

Kontaktwinkel der Monomerflüssigkeit (gegen Zahnschmelz)

η

dynamische Viskosität der Monomerflüssigkeit

r

Kapillarradius (Porenradius)

t

Eindringdauer

Penetration of a liquid (monomer) into a porous solid (enamel lesion) is described physically by the Washburn equation (equation 1, see below). In this equation, it is assumed that the porous solid represents a bundle of open capillaries (Buckton G., Interfacial phenomena in drug delivery and targeting, Chur, 1995); In this case, the penetration of liquid is driven by capillary forces.

d

Distance by which the monomer fluid moves

γ

Surface tension of the monomer liquid (against air)

θ

Contact angle of the monomer liquid (against enamel)

η

dynamic viscosity of the monomer liquid

r

Capillary radius (pore radius)

t

penetration time

PK

Penetrationskoeffizient

γ

Oberflächenspannung der Monomerflüssigkeit (gegen Luft)

θ

Kontaktwinkel der Monomerflüssigkeit (gegen Zahnschmelz)

η

dynamische Viskosität der Monomerflüssigkeit

The bracketed expression of the Washburn Equation is referred to as the Penetration Coefficient (PK, Equation 2, below) ( Fan PL et al., Penetrativity of sealants. J. Dent. Res., 1975, 54: 262-264 ). The PK is composed of the surface tension of the liquid against air (γ), the cosine of the contact angle of the liquid against enamel (θ) and the dynamic viscosity of the liquid (η). The larger the value of the coefficient, the faster the liquid penetrates into a given capillary or porous bed. This means that a high value of PK can be achieved by high surface tension, low viscosity and low contact angle.

PK

penetration coefficient

γ

Surface tension of the monomer liquid (against air)

θ

Contact angle of the monomer liquid (against enamel)

η

dynamic viscosity of the monomer liquid

The Inventors of the present invention have recognized that the inventive Infiltrant not only by a refractive index between 1.53 and 1.65 leads to improved cosmetic results, but At the same time further decisive properties of the infiltrant to improve.

• (a) 50–99 Gew.-% aromatische Monomere,
• (b) bis zu 50 Gew.-% aliphatische Monomere,
• (c) 0,05–5 Gew.-% Initiatoren und
• (d) sonstige dentalübliche Additive.

Preferred infiltrants have the following composition:

• (a) 50-99% by weight of aromatic monomers,
• (b) up to 50% by weight of aliphatic monomers,
• (c) 0.05-5% by weight of initiators and
• (d) other dental additives.

• (a) 55–99 Gew.-% aromatischen Monomeren,
• (b) bis zu 45 Gew.-% aliphatischen Monomeren,
• (c) 0,05–5 Gew.-% Initiatoren und
• (d) sonstigen dentalüblichen Additiven.

The infiltrant according to the invention is further preferably made

• (a) 55-99% by weight of aromatic monomers,
• (b) up to 45% by weight of aliphatic monomers,
• (c) 0.05-5% by weight of initiators and
• (d) other dental additives.

• (a1) 30–99 Gew.-% monocyclisch aromatischen Monomeren,
• (a2) 0–30 Gew.-% polycyclisch aromatischen Monomeren,
• (b) bis zu 70 Gew.-% aliphatischen Monomeren,
• (c) 0,05–5 Gew.-% Initiatoren und
• (d) sonstigen dentalüblichen Additiven.

The infiltrant according to the invention is further preferably made

• (a1) 30-99% by weight of monocyclic aromatic monomers,
• (a2) 0-30% by weight of polycyclic aromatic monomers,
• (b) up to 70% by weight of aliphatic monomers,
• (c) 0.05-5% by weight of initiators and
• (d) other dental additives.

• (a1) 25–99 Gew.-% monocyclisch aromatischen Monomeren,
• (a2) 5–30 Gew.-% polycyclisch aromatischen Monomeren,
• (b) bis zu 70 Gew.-% aliphatischen Monomeren,
• (c) 0,05–5 Gew.-% Initiatoren und
• (d) sonstigen dentalüblichen Additiven.

The infiltrant according to the invention is further preferably made

• (a1) 25-99% by weight of monocyclic aromatic monomers,
• (a2) 5-30% by weight of polycyclic aromatic monomers,
• (b) up to 70% by weight of aliphatic monomers,
• (c) 0.05-5% by weight of initiators and
• (d) other dental additives.

The infiltrant composed according to the invention preferably has a refractive index n _D between 1.55 and 1.60 adapted to an enamel fusion lesion, with a simultaneously high penetration coefficient greater than 50, particularly preferably> 100 cm / s, and a high depth of cure and stress cracking stability.

suitable Aromatic monomers contain derivatives as aromatic groups of benzene, in particular monocyclic or polycyclic aromatic Alcohols, thiols and / or amines.

suitable monocyclic aromatic alcohols are, for example, phenols, cresols, Methoxyphenol, halogenated phenol, alkylphenol, alkoxyphenol, Acetaminophenol, hydroquinone, hydroxycarbazole, mercaptophenol, phenoxyphenol and alkylated and / or halogenated and / or alkoxylated derivatives of these compounds; and benzyl alcohol, p-chlorobenzyl alcohol, p-bromobenzyl alcohol, p-iodobenzyl alcohol, 2,3,4,5,6-pentabromobenzyl alcohol, 2,4,6-trichlorobenzyl alcohol, 2,4,6-tribromobenzyl alcohol, anisalcohol, 2-phenylethyl alcohol, 1-phenylethyl alcohol, 2-thiophenemethanol, N- (2-hydroxyethyl) phthalimide, 4- (methylthio) benzyl alcohol, benzene dimethanol, 1,4-dithiane-2,5-diol, 3,6-dithia-1,8-octanediol, dithiodiethanol, hydroxymethyldithiolane, Furfuryl alcohol, 2- (2-hydroxyethoxy) phenol, N- (2-hydroxyethyl) aniline, N- (2-hydroxyethyl) phthalimide, N- (hydroxymethyl) nicotinamide, N- (hydroxymethyl) phthalimide, N- (3-hydroxypropyl) phthalimide, 2- (3-hydroxypropyl) pyridine, 2-pyridinemethanol, ethyl mandelate, mandelonitrile, 2-mercaptobenzyl alcohol, phenoxyethanol, Phenoxypropanol, 2-phenylethanol, 1-phenyl-2-propanol, 2-phenyl-1-propanol, 3-phenyl-1-propanol, pyridineethanol, pyridinemethanol, pyridinedimethanol, Thiophenemethanol, thiophenethanol and alkylated and / or halogenated and / or alkoxylated derivatives of these compounds.

Examples of suitable polycyclic aromatic alcohols are 1-naphthol, 2-naphthol, brominated naphthol, 9-hydroxyphenanthrene, hydroxypyrene, dihydroxynaphthalene, hydroxyquinoline, 5-indanol, indolol, 4,4'-isopropylidenediphenol, 1-hydroxymethylnaphthalene, 2-hydroxymethylnaphthalene, 1-naphthol. Naphthalenethanol, 2-naphthylethanol, 9-hydroxyfluorene, 1,8-naphthalenedimethanol, 1-acenaphthenol, 9-anthracenemethanol, 2-benzimidazolemethanol, benzoin, 1-benzothiophenesulfo-2-methanol, biphenyldimethanol, biphenylmethanol, 5H-dibenzo [a, d] cycloheptene 5-ol, fluorenylmethanol, fluorenylethanol, fluorenedimethanol, 2- (p-chlorophenyl) ethanol, diphenylethanol, diphenylmethanol, diphenylpropanol, triphenylmethanol, diphenyl-4-pyridylcarbinol, dithiodinaphthol, hydroindantin, hydrobenzoin, hydroxybenzothiazoles, hydroxybenzimidazole, hydroxycoumarins, 9- (2 Hydroxyethyl) -9H-carbazoles, 3- (2-hydroxyethyl) indole, 2-hydroxymethylanthraquinone, 9-hydroxy-9-phenylfluorene, 1-indanol, 2-indanol, indolemethanol, benzylmandelate, 4,4-isopropylidenedi-bis [2- Phenoxyethanol], 4,4-isopropylidenebis [2- (2,6-dibromophenoxy) ethanol], 9,9-bis [4- (2-hydroxyethoxy) phenyl] -fluorenes, bisphenol-A, bisphenol-A-ethylolate, bisphenol F-ethoxylate, benzhydrol, 9-phenyl-9-xanthenol, 9-hydroxyxanthene and alkylated and / or halogenated and / or alkoxylie Derivatives of these compounds.

suitable monocyclic aromatic amines are, for example, aniline, 2-aminothiazole, 2- (2-aminoethyl) thiophene, 2-amino-5- (ethylthio) -1,3,4-thiadiazole, (Aminomethyl) pyridine, aminomethylthiazole, aminophenol, aminopyrazine, Aminopyridine, aminopyrimidine, aminomethylpyridine, benzylamine, diaminotoluene, Phenoxyethylamine, 2-phenylethylamine, 1-phenylpropylamine, 2-phenylpropylamine, 3-Phenylpropylamine, pyridine ethylamine, thiophenemethylamine, and alkylated and / or halogenated and / or alkoxylated derivatives of these compounds.

suitable polycyclic aromatic amines are, for example, 1-naphthylamine, 2-naphthylamine, 2-aminobenzothiazole, 1-amino-4-bromonaphthalene, 2-aminobenzimidazole, aminochryses, [α] -aminodiphenylmethane, Aminoindane, 1- (aminomethyl) naphthalene, aminonaphthol, aminophenanthrene, Aminopyrene, 2-benzylaminopyridine, biphenylethylamine, bis (2-aminophenyl) sulfide, Carbazole, diaminonaphthalene, diphenylethylamine, dithiodinaphthylamine, Furfurylamine, hydrazine, 1- (1-naphthyl) ethylamine, 1- (2-naphthyl) ethylamine, p-phenothiazine, phenoxazine, phenoxyaniline, n-phenyl-1-naphthylamine and alkylated and / or halogenated and / or alkoxylated derivatives of these connections.

aromatic Groups with alkyl, alkoxy or halogen substituents on the ring can be preferred.

Examples particularly suitable aromatic monomers are phenoxyethyl acrylate, Divinylbenzene, benzyl methacrylate or diallyl phthalate.

suitable Aromatic monomers are also aromatic urethanes, preferred aromatic urethane (meth) acrylates.

The Preparation of aromatic urethane monomers is also known per se. It can, for example, by reaction of an aromatic (poly) isocyanate with an isocyanate-reactive compound containing at least one radical polymerizable olefinic unsaturated double bond , preferably a (meth) acrylate group, take place.

When isocyanate-reactive compounds are monomers having at least one isocyanate-reactive group suitable. Suitable, for example Maleinates, fumarates, maleimides, acrylamides, as well as vinyl ethers, propenyl ethers, Allyl ethers, preferred are (meth) acrylates.

suitable Isocyanate-reactive compounds are hydroxy-functional (meth) acrylates for example, selected from the group 2-hydroxyethyl (meth) acrylate, Polyethylene oxide mono (meth) acrylate, polypropylene oxide mono (meth) acrylate, Polyalkylene oxide mono (meth) acrylate, poly-ε-caprolactone mono (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, Hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxy-functional Mono-, di- or tetraacrylates of the polyols, such as trimethylolpropane, Glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, Dipentaerythritol or mixtures thereof.

Farther Isocyanate-reactive oligomers with (meth) acrylate groups are suitable, alone or in combination with suitable monomers. Suitable monomers (Oligomers) are bisphenol-A, bisphenol-F, hexanediol, butanediol or ethoxylated and / or propoxylated derivatives thereof. Glycidyl (meth) acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, Poly ε-caprolactone mono (meth) acrylate or pentaerytrityl triacrylate.

The aromatic urethanes can be alkyl, alkoxy or halogen substituents have directly on the ring.

suitable Examples of (poly) isocyanates are 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate, preferably 1,4-phenylene diisocyanates, 2,4- and / or 2,6-toluene diisocyanate.

suitable Aromatic monomers are also polymerizable groups Esters or amides obtainable from benzenecarboxylic acids, suitable examples of benzene carboxylic acids are benzoic acid, Phthalic acid, isophthalic acid and terephthalic acid.

The aromatic monomers are preferably crosslinking monomers. The aromatic Monomers are preferably monocyclic aromatic monomers.

The aromatic group and at least one, preferably all, polymerizable group (s) are more preferably linked via chain extenders. The chain extension can preferably be achieved by alkoxylation, preferably by ethoxylation or propoxylation. For the chain extension preferably the following linkage options come into question:
Ether bonds, ester bonds, amide bonds and urethane bonds, which in turn can be followed by ethylene glycol or propylene glycol groups.

Preferred chain extenders are, for example, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ - O-CH ₂ -CH ₂ -CH ₂ -, etc .; -O-CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ - CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -O-CO-CH ₂ -CH ₂ -, -O-CO-CH ₂ -CH ₂ -CH ₂ -, -O-CO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -O- CO-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -CO-CH ₂ -CH ₂ -, -CO-CH ₂ -CH ₂ -CH ₂ -, -CO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CO-CH ₂ -CH ₂ - CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -NR ³ -CO-CH ₂ -CH ₂ -, -NR ³ -CO-CH ₂ -CH ₂ -CH ₂ -, -NR ³ -CO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -NR ³ -CO-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -O-CO-NR ³ -CH ₂ -CH ₂ -, -O-CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -, -O-CO-NR ³ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -O-CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -NR ³ -CO-O-CH ₂ -CH ₂ -, -NR ³ -CO-O-CH ₂ -CH ₂ -CH ₂ -, -NR ³ -CO-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -NR ³ -CO-O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -NR ³ -CO-NR ³ -CH ₂ -CH ₂ -, -NR ³ -CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -, -NR ³ -CO-NR ³ -CH ₂ -CH ₂ - O-CH ₂ -CH ₂ -, -NR ³ -CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc., wherein R ^{3 is} preferably H or a methyl group ,

The chain extending group is preferably terminal with the polymerizable group, preferably functionalized (meth) acrylate group.

Examples suitable monocyclic aromatic monomers with chain extender are phenoxyethyl (meth) acrylate or diethoxybenzene di (meth) acrylate, and phenol [2,5EO] (meth) acrylate or dihydroxybenzene [4EO] di (meth) acrylate.

Examples suitable polycyclic aromatic monomers with chain extender are BPA (EO) DMA, ethoxylated bisphenol A dimethacrylate (EO = 1-30); BPA (PO) DMA, propoxylated bisphenol A dimethacrylate (PO = 1-30); BPA (EO) DA, Ethoxylated bisphenol A diacrylate (EO = 1-30); BPA (PO) DA, propoxylated bisphenol A diacrylate (PO = 1-30); BPA (PO) GDA and propoxylated bisphenol A glycerol diacrylate

The monomers having halogen substituents are preferably radiopacity-producing monomers. X-ray opaque monomers in dental materials are known in principle, for example US 4,119,610 A . DE 33 42 601 C1 . EP 0 685 454 B1 . EP 0 710 475 B1 and EP 0 994 844 B1 ,

Examples suitable X-ray opaque aromatic monomers are 2,3-dimethacryloyloxypropyl-1- (2,3,5-triiodobenzoyloxy) propane, 2- [2-iodobenzoyl] ethyl methacrylate or 4,6 dibromo-2-sec-butylphenyl methacrylate.

Especially suitable aromatic monomers are low viscosity and / or in others, low-viscosity monomers readily soluble and / or readily dispersible.

Prefers are aromatic monomers with a dynamic viscosity η <2000 mPas, farther preferably with η <500 mPas, more preferably with η <30 mPas, particularly preferably with η <20 mPas.

The aromatic monomers are at least 30 wt .-%, preferably to at least 50% by weight, more preferably at least 55% by weight, more preferably at least 60 wt .-% in the infiltrant. More preferably, the infiltrant contains 60-90 % By weight of aromatic monomers, more preferably 70-85% by weight.

The monocyclic aromatic monomers are up to in the infiltrant Contain 99 wt .-%, preferably at least 25 wt .-%, more preferably at least 50% by weight, more preferably at least 55% by weight, more preferably at least 70% by weight, more preferably at least 80 wt .-%, more preferably at least 85 wt .-% contained.

polycyclic aromatic monomers with chain extenders are preferred a proportion of up to about 30 wt .-% in the infiltrant be further preferably in a proportion of 10-30 wt .-%, more preferably of 10-25% by weight.

polycyclic aromatic monomers without chain extenders and / or hydroxyl groups comprising 2, 2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane [Bis-GMA] may be present in the infiltrant in small amounts (<20% by weight) but preferably they are not included.

The Aliphatic monomers are monomers with one or crosslinking Monomers having two or more polymerizable groups. According to the invention preferred Aliphatic monomers are the crosslinking monomers.

aliphatic Crosslinking monomers having two polymerizable groups are preferred Derivatives of acrylic and / or methacrylic acid. You can preferably be selected from the group consisting of allyl methacrylate; allyl; PRDMA, 1,3-propanediol dimethacrylate; BDMA, 1,3-butanediol dimethacrylate; BDDMA, 1,4-butanediol dimethacrylate; PDDMA, 1,5-pentanediol dimethacrylate; NPGDMA, neopentyl glycol dimethacrylate; HDDMA, 1,6-hexanediol dimethacrylate; NDDMA, 1,9-nonanediol dimethacrylate; DDDMA, 1,10-decanediol dimethacrylate; DDDDMA, 1,12-dodecanediol dimethacrylate; PRDA, 1,3-propanediol diacrylate; BDA, 1,3-butanediol diacrylate; BDDA 1,4-butanediol diacrylate; PDDA, 1,5-pentanediol diacrylate; NPGDA, neopentyl glycol diacrylate; HDDA, 1,6-hexanediol diacrylate; NDDA, 1,9-nonanediol diacrylate; DDDA, 1,10-decanediol; DDDDA, 1,12-dodecanediol dimethacrylate; EGDMA, ethylene glycol; DEGDMA, diethylene glycol dimethacrylate; TEDMA, triethylene glycol dimethacrylate; TEGDMA, tetraethylene glycol dimethacrylate; EGDA, ethylene glycol diacrylate; DEGDA, diethylene glycol diacrylate; TEDA, triethylene; TEGDA, tetraethylene glycol diacrylate; PEG200DMA, Polyethylene glycol 200 dimethacrylate; PEG300DMA, polyethylene glycol 300 dimethacrylate; PEG400DMA, polyethylene glycol 400 dimethacrylate; PEG600DMA, polyethylene glycol 600 dimethacrylate; PEG200DA, polyethylene glycol 200 diacrylate; PEG300DA, polyethylene glycol 300 diacrylate; PEG400DA, Polyethylene glycol 400 diacrylate; PEG600DA, polyethylene glycol 600 diacrylate; PPGDMA, polypropylene glycol dimethacrylate; PPGDA, polypropylene glycol diacrylate; NPG (PO) 2DMA, propoxylated (2) neopentyl glycol dimethacrylate; NPG (PO) 2DA Propoxylated (2) neopentyl glycol diacrylate; UDMA, diurethane dimethacrylate; TCDDMA, tricyclo [5.2.1.0] decanedimethanol dimethacrylate; TCDDA, tricyclo [5.2.1.0] decanedimethanol diacrylate; EBA, ethylenebisacrylamide; DHEBA, N, N '- (1,2-dihydroxyethylene) bisacrylamide; DEPBA, N, N'-diethyl (1,3-propylene) bisacrylamide; TMHMBMA, N, N '- (2,2,4-trimethylhexamethylene) bismethacrylamide; and Bis [2- (2-methylacrylamino) ethoxycarbonyl] hexamethylene diamine.

Preferred aliphatic crosslinking monomers having more than two polymerizable groups have the following formula R 1 [X k R 2 l Y m ] n on, with the following meanings
R ¹ is a linear or branched hydrocarbon having 3-24 C atoms, containing alkyl or cycloalkyl;
optionally containing O, N, Si, S, P as heteroatoms, for example siloxane and / or cyclosiloxane and / or carbosilane and / or cyclocarbosilane and / or in particular ether or polyether groups, polyester groups, polysiloxane groups or polycarbosilane groups;
optionally substituted by hydroxyl and / or carbonyl and / or halogen (preferably fluorine) and / or ammonium alkylene groups and / or siloxane and / or cyclosiloxane and / or carbosilane and / or cyclocarbosilane;
R ² is a linear or branched hydrocarbon having 1-16 C atoms, containing alkyl or cycloalkyl;
optionally containing O, N, Si, S, P as heteroatoms, for example siloxane and / or cyclosiloxane and / or carbosilane and / or cyclocarbosilane and / or in particular ether or polyether groups, polyester groups, polysiloxane groups or polycarbosilane groups;
optionally substituted by hydroxyl and / or carbonyl and / or halogen (preferably fluorine) and / or ammonium alkylene groups and / or siloxane and / or cyclosiloxane and / or carbosilane and / or cyclocarbosilane;
X is a linking group, identically or differently selected, from an ether group, carbonyl group, ester group, amide group, urethane group or urea group;
Y is a group identical or different, containing a polymerizable double bond and / or a ring polymerizable group and / or a thiol group and / or an epoxide group and / or a vinyl, preferably (meth) acrylate and / or (meth) acrylamide;
k is 0 or 1; 1 is 0 or 1; m is at least 1; n is at least 1; m × n is at least 3.

It may be beneficial if the monomers are additional functional Groups such as ammonium alkylene groups or fluorinated alkylene.

suitable aliphatic low-viscosity monomers having at least three polymerizable Examples of groups are glycerol triacrylate, TMPTMA, trimethylolpropane trimethacrylate, TMPTA, trimethylolpropane tri (meth) acrylate; DTMPTA; Di-Trimethylolpropantetra (meth) acrylate; DiPENTA, di-pentaerythritol penta (meth) acrylate; or DPEHA, di-pentaerythritol hexa (meth) acrylate.

preferred aliphatic low-viscosity monomers having at least three polymerizable For example, groups are based on alkoxylated multiple alcohols (tri, Tetra-, penta, hexa, polyols) such as trimethylolpropane, ditrimethylolpropane, Glycerol, pentaerythritol or dipentaerythritol.

Especially preferred are (meth) acrylic esters of alkoxylated multiple alcohols such as ethoxylated glycerol triacrylate, propoxylated Glycerol triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated Trimethylolpropane triacrylate, propoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol trimethacrylate, ethoxylated pentaerythritol triacrylate, ethoxylated pentaerythritol tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated di-pentaerythritol trimethacrylate, ethoxylated di-pentaerythritol tetramethacrylate, ethoxylated Di-pentaerythritol pentamethacrylate, ethoxylated di-pentaerythritol hexamethacrylate, ethoxylated di-pentaerythritol triacrylate, ethoxylated di-pentaerythritol tetraacrylate, ethoxylated di-pentaerythritol-pentaacrylate, ethoxylated di-pentaerythritol-hexaacrylate, propoxylated pentaerythritol trimethacrylate, propoxylated pentaerythritol triacrylate, propoxylated pentaerythritol tetramethacrylate, propoxylated Pentaerythritol tetraacrylate, propylated di-pentaerythritol trimethacrylate, propoxylated di-pentaerythritol tetramethacrylate, propoxylated Di-pentaerythritol pentamethacrylate, propoxylated di-pentaerythritol hexamethacrylate, propoxylated di-pentaerythritol triacrylate, propoxylated di-pentaerythritol tetraacrylate, propylated di-pentaerythritol pentaacrylate, propoxylated di-pentaerythritol hexaacrylate.

Such attached to the alcohols put alkoxy groups (molecule) Chain extender. The chain extension can preferably be achieved by ethoxylation or propoxylation become. For the chain extension come more Linking possibilities, for example, ether bonds, Ester bonds, amide bonds, urethane bonds and the like in Question, to which in turn preferred ethylene glycol or propylene glycol groups can connect.

Preferred chain extenders are, for example, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ - O-CH ₂ -CH ₂ -CH ₂ -, etc .; -O-CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -O-CH ₂ -CH ₂ - CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -O-CO-CH ₂ -CH ₂ -, -O-CO-CH ₂ -CH ₂ -CH ₂ -, -O-CO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -O- CO-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -CO-CH ₂ -CH ₂ -, -CO-CH ₂ -CH ₂ -CH ₂ -, -CO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CO-CH ₂ -CH ₂ - CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -NR ³ -CO-CH ₂ -CH ₂ -, -NR ³ -CO-CH ₂ -CH ₂ -CH ₂ -, -NR ³ -CO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -NR ³ -CO-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -O-CO-NR ³ -CH ₂ -CH ₂ -, -O-CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -, -O-CO-NR ³ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -O-CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -NR ³ -CO-O-CH ₂ -CH ₂ -, -NR ³ -CO-O-CH ₂ -CH ₂ -CH ₂ -, -NR ³ -CO-C-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -NR ³ -CO-O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc .; -NR ³ -CO-NR ³ -CH ₂ -CH ₂ -, -NR ³ -CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -, -NR ³ -CO-NR ³ -CH ₂ -CH ₂ - O-CH ₂ -CH ₂ -, NR ³ -CO-NR ³ -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -CH ₂ -, etc., wherein R ^{3 is} preferably H or a methyl group.

The chain extending group is preferably terminal with the crosslinking groups, preferably a methacrylate, a Acrylate group, methacrylamide or acrylamide functionalized.

By Chain extender enlarges the Chain length of a molecule is preferably such that the distance of its crosslinking points at least 7, preferably at least 9, more preferably 10 to 30, particularly preferably 11 to 21 bond lengths is. The distance is preferably less as 50 bond lengths.

When Crosslinking point is the position of the crosslinking polymerizable For example, group considered the position of a C = C double bond in the monomer.

With Distance of the crosslinking points, is the shortest distance the crosslinking groups, for example, of two C = C double bonds along to understand the molecule. So it's just the constitution of the molecule, not the real spatial one Location of the groups to each other, for example by configuration or conformation conditionally.

Under Binding length is the distance between two atoms in the molecule no matter what type of covalent bond is present and which exact bond length has the single covalent bond.

By the setting of a distance between the crosslinking groups a monomer as defined above and concomitant adjustment a corresponding net arc length in crosslinked polymers can reduce the stresses in the cured polymer be reduced. This reduction in voltages leads to that it also under thermal cycling such as a thermocycling used as a test method between 5 and 55 ° C not to stress-induced cracking in the polymer comes. The mechanical properties and in particular the durability of the hardened infiltrant are thus improved.

Of the preferred proportion of these monomers depends on the number of crosslinking groups in monomer mix, size the chain-extending groups and the resulting PK off.

suitable aliphatic monomers having a polymerizable group preferably be selected from the group consisting of MMA, methyl methacrylate; EMA, ethyl methacrylate; n-BMA, n-butyl methacrylate; IBMA, isobutyl methacrylate, t-BMA, tert-butyl methacrylate; EHMA, 2-ethylhexyl methacrylate; LMA, lauryl methacrylate; TDMA, tridecyl methacrylate; SMA, stearyl methacrylate; CHMA, cyclohexyl methacrylate; BZMA, benzyl methacrylate; IBXMA, isobornyl methacrylates; HEMA, 2-hydroxyethyl methacrylate; HPMA, 2-hydroxypropyl methacrylate; DMMA, dimethylaminoethyl methacrylate; DEMA, diethylaminoethyl methacrylate; GMA, glycidyl methacrylate; THFMA, tetrahydrofurfuryl methacrylate; AMA, allyl methacrylate; ETMA, ethoxyethyl methacrylate; 3FM, trifluoroethyl methacrylate; 8FM, octafluoropentyl methacrylate; AIB, isobutyl acrylate; TBA, tert-butyl acrylate; LA, lauryl acrylate; CEA, cetyl acrylate; STA, stearyl acrylate; CHA, cyclohexyl; IBXA, isobornyl acrylate; 2-MTA, 2-methoxyethyl acrylate; ETA, 2-ethoxyethyl acrylate; EETA, ethoxyethoxyethyl acrylate; THFA, tetrahydrofurfuryl; HEA, 2-hydroxyethyl acrylate; HPA, 2-hydroxypropyl acrylate; 4HBA, 4-hydroxybutyl acrylate; DMA, dimethylaminoethyl acrylate; 3F, trifluoroethyl; 17F, heptadecafluorodecyl acrylate; TBCH, 4-tert-butylcyclohexyl acrylate; DCPA, dihydrodicyclopentadienyl acrylate; EHA, 2-ethylhexyl acrylate; and 3EGMA, triethylene glycol monomethacrylate.

The Aliphatic monomers are preferably of low viscosity. The aliphatic Monomers preferably have a dynamic viscosity η <50 mPas, farther preferably with η <20 mPas, more preferably with η <10 mPas, particularly preferably with η <5 mPas.

Of the Infiltrant may contain up to 70% by weight of aliphatic monomers. Preference is given in the infiltrant up to 50 wt .-%, more preferably up to 45% by weight, more preferably up to 30% by weight in the infiltrant. More preferably, the infiltrant contains 10-45 Wt .-%, even more preferably 15-30 wt .-% aliphatic Monomers.

suitable Aliphatic or aromatic monomers may also be acid groups contain. Suitable acid groups are carbon, sulfone, Phosphoric and phosphonic acid groups. For example, can it is in addition to having acid groups listed above in particular aliphatic (meth) acrylates act. Particularly preferred is methacryloyloxydecyl dihydrogen phosphate (MDP).

Of the Infiltrant can contain 0.05-20% by weight of acid group Contain monomers. The content of acid group-containing However, monomers is preferably 0.5-2 wt .-%.

Of the Proportion of crosslinking monomers based on the totality of the monomers in the infiltrant can be 100 to 50 wt .-%, preferably 100 to 80 Wt .-%, more preferably 100 to 90 wt .-%, more preferably 100 wt .-% amount.

Of the Proportion of crosslinking monomers with at least three polymerizable Groups, based on the total of all monomers in the infiltrant, may preferably be between 0 and 50% by weight, more preferably 10 and 30 wt .-% are.

The proportion of crosslinking monomers having at least three polymerizable groups and a The distance of the crosslinking points of less than 10 bond lengths, based on the total mass of the monomers, is preferably less than 20 wt .-%, more preferably less than 10 wt .-%, more preferably less than 5 wt .-%.

The Infiltrants according to the invention can each be according to the chemical structure of the monomers contained, preferably radically, cure anionic or cationic. Particularly preferred the monomers curable radically or cationically.

The radical curing of the monomers according to the invention can be carried out by vinyl polymerization of suitable double bonds. Particularly suitable here are (meth) acrylates, (meth) acrylamides as they are, for example, in the EP 1674066 A1 and the EP 1974712 A1 are disclosed, styryl compounds, cyanoacrylates and compounds with similarly good free-radically polymerizable double bonds. Another possibility of free-radical curing is the ring-opening polymerization of cyclic vinyl compounds such as those in EP1413569 . EP1741419 and EP1688125 described vinylcyclopropanes or other cyclic systems such as vinylidene-substituted Orthospirocarbonaten or Orthospiroestern. A further possibility also exists in the copolymerization of the ring-opening polymerizing systems with the abovementioned singly polymerizing double bonds.

In addition, radical curing can be achieved by a step reaction known from the term thiol-ene reaction, as in US Pat WO 2005/086911 described, done.

The cationic curing of the monomers according to the invention can likewise be carried out by ring-opening or by vinyl polymerization. Suitable vinyl polymers are vinyl ethers, styryl compounds and other compounds having electron-rich vinyl groups. Suitable ring-opening polymerizing monomers are known to those skilled compounds, for example, epoxy, oxetane, aziridine, oxazoline or Dioxolangruppen etc .. Particularly suitable are silicon-containing epoxy monomers, as in WO 02/066535 or WO 2005/121200 are described. Particularly advantageous in the use of epoxides or oxetanes is the low polymerization shrinkage as well as the low inhibition layer of these materials.

Of the Infiltrant contains those known in the art and in the dental field customary initiators, in particular light-activated Initiator systems or chemically activating initiators or mixtures of different systems.

The here usable initiators can, for. B. photoinitiators be. These are characterized by their absorption of light in the wavelength range from 300 nm to 700 nm, preferably from 350 nm to 600 nm and more preferably from 380 nm to 500 nm and optionally by the additional reaction with one or more coinitiators, the curing of the material can effect. Preference is given here phosphine oxides, Bezoinether, Benzil ketals, acetophenones, benzophenones, thioxanthones, bisimidazoles, Metallocenes, fluorones, α-dicarbonyl compounds, aryldiazonium salts, Arylsulfonium salts, aryliodonium salts, ferrocenium salts, phenylphosphonium salts or a mixture of these compounds used.

Especially preference is given to diphenyl-2,4,6-trimethylbenzoylphosphine oxide, benzoin, Benzoin alkyl ethers, benzil dialkyl ketals, α-hydroxy acetophenone, Dialkoxyacetophenones, α-aminoacetophenones, i-propylthioxanthone, Camphorquinone, phenylpropanedione, 5,7-diiodo-3-butoxy-6-fluorone, (eta-6-cumene) (eta-5-cyclopentadienyl) iron hexafluorophosphate, (eta-6-cumene) (eta-5-cyclopentadienyl) iron tetrafluoroborate, (Eta-6-cumene) (eta-5-cyclopentadienyl) iron hexafluoroantimonate, substituted diaryliodonium salts, triarylsulfonium salts or a Mixture of these compounds used.

When Co-initiators for a photochemical curing tertiary amines, borates, organic phosphites, Diaryliodonium compounds, thioxanthones, xanthenes, fluorenes, fluorones, α-dicarbonyl compounds, condensed polyaromatics or a mixture of these compounds used. Particular preference is given to N, N-dimethyl-p-toluidine, N, N-dialkyl-alkyl-anilines, N, N-dihydroxyethyl-p-toluidine, 2-ethylhexyl-p- (dimethyl-amino) -benzoate, Butyrylcholine-triphenylbutylborate, N, N-dimethyl-4-tert-butylaniline, N, N-diethyl-3,5-di-tert-butylaniline, 4-tert-butylaniline or a mixture of these compounds used.

To 100 parts of monomer mixture are preferably 0.05 to 2 parts Photoinitiator added, more preferably 0.1 to 1 parts. coinitiator is contained in excess, 1-5 times, preferably 1-3 times, based on the initiator.

Of the Infiltrant can be made from a kit with at least two components become. Two-component infiltrants have the advantage that they are self-curing (chemical curing) can be designed. In one embodiment contains a first component monomers and chemically activated Initiators and a second component suitable activators.

For a chemical curing at room temperature i. a. uses a redox initiator system consisting of one or more Initiators and serving as an activator coinitiator or coinitiators consists. For reasons of storage stability Initiator or initiators and coinitiator or coinitiators in spatially separate parts of the invention Infiltrants incorporated, d. H. it is a multi-component, prefers a two-component material. As initiator or Initiators are preferably inorganic and / or organic peroxides, Inorganic and / or organic hydroperoxides, barbituric acid derivatives, Malonylsulfamides, protonic acids, Lewis or Broensted acids or compounds that release such acids, carbenium ion donors such as As methyl triflate or triethyl perchlorate or a mixture from these compounds and as a coinitiator or as coinitiators preferably tertiary amines, heavy metal compounds, in particular Compounds of the 8th and 9th group of the periodic table ("iron ore and copper group "), compounds with ionogenically bound Halogens or pseudohalogens such. B. quaternary ammonium halides, weak Broenstedt acids such. As alcohols and water or a mixture of these compounds used.

Of the Infiltrant may still contain radiopaque organic metal compounds contain. The radiopaque metal compounds are in particular soluble in the infiltrant and / or easily distributed. Especially suitable are monomers such as, for example, metal acrylates and methacrylates. Suitable metals for this purpose have the atomic number 30 and above, preferably 30 to 79. The metals are particularly preferably strontium, Yttrium, zirconium, hafnium, zinc and selected lanthanides, eg Ytterbium.

The monomeric metal compounds may also be prepolymerized become. The infiltrant then contains the resulting Polymers or preferably oligomers in dissolved form.

preferred Metallic compounds are, for example, strontium di (meth) acrylate, yttrium tri (meth) acrylate, Zirconium tetra (meth) acrylate, zirconyl di (meth) acrylate, zirconium carboxyethyl acrylate, Hafnium carboxyethyl acrylate, zinc di (meth) acrylate and the like. s. w.

Of the Infiltrant contains preferably> 20 wt .-% radiopaque metal compounds, particularly preferably> 30 Wt .-%.

The infiltrant determines an X-ray opacity determined ISO 4049 of at least 100% by weight, more preferably at least 150% by weight, particularly preferably at least 200% of aluminum.

The Monomer mixtures and / or infiltrants preferably have a dynamic Viscosity less than 20 mPas, more preferably less than 15 mPas, more preferably less than 10 mPas.

The Monomer mixtures or the infiltrant preferably have small contact angles θ Tooth enamel, preferably θ <60 °, more preferably θ <25 °, am most preferred is θ <10 °.

The Monomers or the infiltrant preferably exhibit a surface tension γ> 30 mN / m.

The Mixture of different monomers is used in particular also the Coordination of mechanical properties such as hardness and Strength, the depth of cure or the degree of polymerization, the residual monomer content, the smear layer characteristic, shrinkage, stability, water absorption and in particular the absence of tension while maintaining a high penetration capacity (PK> 100).

The infiltrant can also be the expert from eg WO 02/062901 . WO 2006/031972 or EP 1714633 known and commonly used in the dental field hyperbranched monomers, for example. Dendrimers have, in particular to reduce the residual monomer content and to improve the biocompatibility.

The infiltrant may, for example, the expert from EP 1285947 or EP 1849450 contain known and common in the dental field bactericidal monomers.

Of the Infiltrant particularly preferably consists essentially of monomers and polymerization initiator.

The Monomer mixtures or the infiltrant preferably have one PK> 100, preferably> 150, particularly preferably> 200 cm / s.

Of the Infiltrant may be more common in the dental profession known to those skilled in the art Additives, such as stabilizers, solvents, bacteriostats or bactericides, fluoridation agents, dyes and the like. s. w. contain. The additives are preferably in the (crosslinking) monomers of Infiltrants soluble.

Among the stabilizers, UV stabilizers are preferred. Suitable UV stabilizers are known to the skilled artisan is exemplified herein Chimasorb ^® and Tinuvin ^® (Ciba).

Under the solvents become medium-volatile solvents such as alcohols, ketones and ethers and esters, u. s. w. prefers. Particularly preferred are alcohols, especially ethanol or solvents with similar Evaporation behavior. Preferred solvents have at RT has a vapor pressure approximately between that of 2-propanone (-246 hPa (20 ° C)) and that of water (-23 hPa (20 ° C)), preferably between 30 and 250 hPa (20 ° C, atmospheric pressure).

Prefers the infiltrant contains less than about 10 Mass%, more preferably less than about 5 mass%, most preferably no solvent.

Among the dyes, fluorescent dyes are preferred in order to further improve the appearance or to better match the natural tooth enamel. Suitable fluorescent colorants are known in the art and, for example, in the US 2004/017928 A1 described. Further suitable are colorants for the preparation of various tooth colors, the color changing dyes, to indicate the infiltrated lesion or the hardening of the infiltrant. Preferably, the dye is colorless after curing of the infiltrant. The dye can be radically reactive. The color change can also depend on other influences, for example on the pH. The dye may have adsorptive properties, especially with respect to the enamel, so that it accumulates in the upper layer of the lesion. The color change can then be seen better in the interdental region. The dye may have non-adsorptive properties and penetrate deeply into the lesion, so that, for example, the penetration can be better controlled.

Of the Infiltrant preferably contains less than about 10% by weight Additives, more preferably less than 5 wt .-%, even more preferred less than 2% by weight.

• 1. Entfernen einer dünnen Oberflächenschicht der Schmelzläsion (durch Ätzmittel)
• 2. Abspülen des Ätzmittels (optional)
• 3. Trocknen der Läsion (mit einem Trocknungsmittel)
• 4. Infiltration der Läsion mit einem Infiltranten
• 5. Entfernen von Überschüssen (optional)
• 6. Härten des Infiltranten
• 7. Infiltration der Läsion mit einem Infiltranten (optional)
• 8. Entfernen von Überschüssen (optional)
• 9. Härten des Infiltranten (optional)
• 10. Politur der infiltrierten Läsionsoberfläche (optional)

The invention further relates to the use of an infiltrant according to the invention for the treatment and / or prevention of carious enamel lesions. Such use may include the following steps:

• 1. Removal of a thin surface layer of enamel lesion (by etchant)
• 2. Rinse off the etchant (optional)
• 3. Drying of the lesion (with a drying agent)
• 4. Infiltration of the lesion with an infiltrant
• 5. Removal of surpluses (optional)
• 6. Hardening of the infiltrant
• 7. Infiltration of the lesion with an infiltrant (optional)
• 8. Removing surpluses (optional)
• 9. Hardening of the infiltrant (optional)
• 10. Polish the infiltrated lesion surface (optional)

Preferably, the surface layer of the enamel lesion is removed by etchant, such as, for example, from published International patent applications WO 07/131725 A1 . WO 2009/124671 A1 or WO 2009/124672 A1 are known.

However, it is also possible to mechanically remove the surface layer of the enamel lesion, in combination with etchants or exclusively, preferably by means of rotating instruments present in the dental practice. In this case, aids such as polishing pastes can be used. For example, the Prema ^® Microabrasion paste kit of Premier Dental Products Company may be used.

Preferred drying agents are toxicologically harmless solvents with high vapor pressure. Desiccants with a vapor pressure greater than that of water (23 mbar [20 ° C.]) are particularly preferred. These are, for example, selected from alcohols, ketones, ethers, esters, etc. Particularly preferred Ethanol.

The Desiccant may contain components of the initiator system, which remain in the lesion after its evaporation.

The Desiccant may contain a film former.

• 1. Ätzmittel
• 2. Trocknungsmittel (optional)
• 3. Infiltrant.

The invention further comprises a kit for carrying out the infiltration process. This includes

• 1. Etching agent
• 2. Desiccant (optional)
• 3. Infiltrant.

in the The invention is explained below with reference to some examples.

Monomer mixtures were prepared and their refractive index (n _D ), color (ΔE), penetration coefficient (PK), depth of cure (DHT) and mechanical behavior were checked.

The following components were used: TEDMA Triethlenglycoldimethacrylat Miramer ^® M3130 Trimethylolpropane ethoxylated with avg. 1 ethoxy units per methylol group and terminally acrylated Miramer ^® M140 phenoxyethyl Miramer ^® M202 1,6-hexanediol ethoxylated with avg. 1 EO unit per hydroxyl group and terminal acrylated EBPADMA Bis-phenol-A ethoxylated with avg. 1 EO unit per hydroxy group and terminally methacrylated Bis-GMA 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane MMA methyl methacrylate CQ camphorquinone EHA Ethylhexyl pN, N-dimethylaminobenzoate BHT 2,6-di-tert-butyl phenol

test methods

surface tension

The Surface tension of the resins was determined by contour analysis hanging drop (DSA 10, KRÜSS GmbH). The measurement of the surface tension was on newly formed drops over a period of time 30 s, with a measured value recorded approximately every 5 s has been. For this purpose, the resins were applied with a fine syringe and the forming drop filmed with a digital camera. Out the characteristic shape and size of the drop became the surface tension according to the Young-Laplace equation certainly. For each resin so 3 measurements were made, the mean value of which was given as the surface tension.

contact angle

For each individual measurement was used enamel from bovine teeth. For this purpose, bovine teeth were embedded in a synthetic resin and the melt surface by means of a grinding machine (Struers GmbH) with sandpaper (80, 500 and 1200 grit) wet Polished, so that plane about 0.5 × 1.0 cm in size Melting surfaces for contact angle measurements were available. The enamel samples were added to the Measurement stored in distilled water and with before measurement Ethanol and compressed air dried.

The measurement of the contact angle was carried out with the aid of a video contact angle measuring device (DSA 10, KRÜSS GmbH). Here, a drop of the resin mixture was placed on the melt surface by means of a microliter syringe, recorded within 10 seconds up to 40 individual images of the droplet under computer control and determined by drop contour analysis software, the contact angle. Equipment and materials had room temperature temperature (23 ° C).

Dynamic viscosity

The dynamic viscosity, which is also referred to as absolute viscosity, is a measure of the viscosity of a liquid medium and is expressed by the viscosity constant η with the units Pas and Ns / m2. The greater the viscosity constant η the less fluid is a liquid. The viscosity depends on the temperature. The infiltrants according to the invention are liquids which contain no components which would produce an intrinsic viscosity and thus reduce the ability to penetrate. The infiltrants according to the invention are thus Newtonian fluids. Their dynamic viscosity is a material constant at a given temperature. It does not depend on the shear rate, as is characteristic of non-Newtonian fluids (see, for example, US Pat ISO 3219: 1993 , Number 3 on page 1 under "Notes").

The Viscosity of the resins was at 23 ° C (room temperature) using dynamic plate-plate viscometers (Dynamic Stress Rheometer, Rheometric Scientific Inc.). It was in the "Steady Stress sweep "mode at gap sizes of 0.1 to 0.5 mm in the range of 0 to 50 Pa shear stress without shearing the resins measured.

Depth of Cure

The through-cure depths of the resins softened according to the "polymerization depth" test ISO 4049: 2000 certainly. For this purpose, the resins were filled into cylindrical Teflon molds (5 mm in diameter, 10 mm high) and exposed with a halogen lamp (Translux EC, Heraeus Kulzer GmbH) for 15 or 20 s from above. Immediately after the exposure, the cured specimens were demolded and freed from uncured material with a plastic spatula. The height of the hardened cylindrical cone was given as the depth of cure (DHT).

(Thermomechanical testing) Stress cracking stability

The verification the thermomechanical load capacity of the cured Infiltrants were carried out by means of cylindrical test specimens (∅25 × 2.5 mm). The test specimens were prepared by the respective infiltrants in corresponding Shaping for 5 minutes in a light curing unit (illuminance 15200 lux) and then at 40 ° C for 23 h stored in a drying oven.

The Test specimens were subjected to a temperature change (thermocycler, Willytec) exposed by alternating in water baths were immersed at temperatures of 55 ° C and 5 ° C. The immersion time was 30 s, the dripping time 10 each s, so a dive cycle lasted 40 seconds. The test specimens 5000 diving cycles were suspended. Subsequently the test specimens were cracked and microcracked examined.

refractive index

The The refractive index of the infiltrants was determined by means of a degradation refractometer AR (A. Krüss Optronik) at 23 ° C ± 0,5 ° C determined against air based on the D-line of sodium light.

To determine the refractive index of the cured infiltrants, 2 specimens of each infiltrant were prepared. For this purpose, the infiltrant was introduced (20 × 0.5 mm × 80) each in a steel mold, which slides on a covered with a clear, colorless polyester film (Hostaphan ^®) was positioned. Another foil, followed by another slide was bubble exposed to the resin attached with terminals and by means of light-curing unit (Heraflash ^®; Heraeus Kulzer) exposed for 90 sec. Subsequently, the cured specimen was removed from the mold. The specimens were stored for 4 days at 23 ° C and 50% humidity. The refractive index was after ISO 489: 1999 determined using the Abberefractometer AR (A. Krüss Optronik). One drop of bromonaphthalene is added to the specimen and brought into contact with the measuring prism of the refractometer. From the read refractive indices (4 digits) the mean value was calculated for each infiltrant.

color difference

From the labial surfaces of extracted bovine incisors, two enamel samples (5 × 4 × 3 mm) were prepared with constant water cooling (band saw Exakt 300 cl, Exakt Apparatebau, Nor derstedt, Germany). With the help of silicone molds, the samples were embedded in synthetic resin (Technovit 4071, Heraeus Kulzer, Hanau, Germany) and then sandblasted by a polishing machine (Phoenix Alpha, Buehler, Dusseldorf, Germany) (1200 grit sandpaper, 2400 grit paper) Exakt Apparatebau standardized and polished the sample surfaces on the thus prepared enamel samples, two strips each were covered with nail varnish to serve as a healthy control later on, with each sample showing two unprotected enamel surfaces Heraeus Kulzer) was subjected to a demineralization solution [Buskes et al., 1985] (pH = 4.95) at 37 ° C. (hot pot BR 6000, Heraeus Kulzer) for a period of 50 days using a pH meter (pH / redox / temperature). GMH 3510, Greisinger, Regenstauf, Germany), the pH was checked daily and in the case of a deviation from the nominal value with small amounts of potassium rectified with 10 ml of hydrochloric acid solution (10 M) and topped up with hydrochloric acid (10%). The nail polish was carefully removed using compressed air. Subsequently, the areas 3 and 4 (lesion + healthy) of the moist samples were etched with 37% phosphoric acid (Ivoclar Vivadent) for 2 seconds. The etchant was then rinsed thoroughly under running water for 30 s. The samples were freed by ethanol application and subsequent drying of residual moisture. After repeated drying, the various plastics were applied for 30 s, excesses were removed with a cotton roll and light-cured for 60 s (n = 20 / group). Thereafter, the materials were applied a second time for 30 s, then the surplus was removed and the plastic was light-cured. Under standardized conditions, digital photographs were taken of the samples. For this purpose, a single-lens reflex camera (Canon EOS 40D) was used, which was equipped with a 100 mm fixed focal length macro lens and a Canon MR-14EX ring flash. To standardize the illumination of the samples, a light-tight box was constructed, in which a sample holder, as well as 2 stands (for the camera body and the macro lens) were installed. In order to avoid reflections of the light and to achieve the widest possible scattering of the light, the inner walls of the box were lined with dark acoustic nub foam. The settings of the camera were made manually to eliminate automatic corrections of the camera. The flash controller is powered by Ni-Mh 2650 mAh batteries, ensuring a consistent level of lightning from capacitors built into the controller. In this context, care was taken to give the flash tubes enough time to cool between the flashes so that heating and thus a change in the light temperature could be avoided. The photographic reference point for setting the white balance was a gray card that surrounded the sample holder in the manner of a Passepar touts and was therefore included on each photograph. The distinction between the states "moist" and "dry" was defined as follows: "moist" corresponds to the just removed from the solution and only to avoid reflections superficially briefly dried sample, the "dry" state after 10 minutes of storage in air was achieved. The post-processing and evaluation of the images was done with a photo editing software (Photoshop CS 4 extended). To calibrate the images, the white balance was adjusted in the original RGB format and the image was then converted to L * a * b format for further processing. The color values were measured in the L * a * b color space. Each sample area (1-4) was measured in a range defined for each sample. The difference in tooth color to the untreated healthy control (area 2) was calculated using the formula: ΔE * = √ (ΔL *) ² + (Δa *) ² + (Δb *) ² .

description the preparation of example and reference example compositions.

The Example compositions 1-13 were according to Table prepared by stirring the appropriate components. For the investigations of the hardening depth and Refractive index, the amounts of CQ indicated for the resin mixtures were EHA and BHT added. All mixtures were up to the optically clear Solution stirred.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 07/131725 A1 [0004, 0112]
• WO 2007/131725 A1 [0008]
• - DE 202008006814 U1 [0008]
• - US 4119610 A [0049]
• - DE 3342601 C1 [0049]
• EP 0685454 B1 [0049]
• - EP 0710475 B1 [0049]
• EP 0994844 B1 [0049]
• - EP 1674066 A1 [0082]
• EP 1974712 A1 [0082]
• - EP 1413569 [0082]
• - EP 1741419 [0082]
• - EP 1688125 [0082]
• WO 2005/086911 [0083]
• WO 02/066535 [0084]
• WO 2005/121200 [0084]
• WO 02/062901 [0101]
• WO 2006/031972 [0101]
• EP 1714633 [0101]
• EP 1285947 [0102]
• EP 1849450 [0102]
• US 2004/017928 A1 [0109]
• WO 2009/124671 A1 [0112]
• WO 2009/124672 A1 [0112]

Cited non-patent literature

• - Paris S, Meyer-Lückel H: Masking of labial enamel White spot lesions by resin infiltration - A clinical report; Quintessence Int 2009, 40, 713-718 [0005]
• - ISO 489: 1999 [0010]
• - Fan PL et al., Penetrativity of sealants. J. Dent. Res, 1975, 54. 262-264 [0021]
• - ISO 4049 [0096]
• - ISO 3219: 1993 [0124]
• - ISO 4049: 2000 [0126]
• - ISO 489: 1999 [0130]

Claims (11)

Infiltrant for the treatment of an enamel lesion consisting of, a) 30-99% aromatic monomers, b) 0-70% aliphatic monomers, c) 0.05-5% initiators and d) other dental additives, the infiltrant being incubated at room temperature (23 ° C) C) having a penetration coefficient PK according Washburn equation is greater than 50 cm / s and a refractive index n _D in the hardened state from 1.53 to 1.65. Infiltrant according to claim 1, consisting of a) 55-99% by weight of aromatic monomers, b) up to 45 % By weight of aliphatic monomers, c) 0.05-5 wt .-% initiators and d) other dental additives. Infiltrant according to claim 1, consisting of (A1) 30-99% by weight of monocyclic aromatic monomers, (A2) 0-30% by weight of polycyclic aromatic monomers, (E) up to 70% by weight of aliphatic monomers, (f) 0.05-5 Wt .-% initiators and (g) other usual dental Additives. Infiltrant according to claim 1, consisting of (A1) 25-99% by weight of monocyclic aromatic monomers, (A2) 5-30% by weight of polycyclic aromatic monomers, (B) up to 70% by weight of aliphatic monomers, (c) 0.05-5 Wt .-% initiators and (d) other usual dental Additives. Infiltrant according to Claim 1, characterized the aliphatic monomers are crosslinking. Infiltrant according to Claim 1, characterized that the aromatic monomers, at least 20 wt .-% crosslinking are. Infiltrant according to Claim 1, characterized that the monomers contain at least one chain extender. Infiltrant according to claim 1, characterized in that the refractive index n _{D is} between 1.55 and 1.60. Infiltrant according to Claim 1, characterized the penetration coefficient PK is> 100 cm / s. Infiltrant according to claim 1 for the treatment of dental caries. Kit for the treatment of dental caries containing 1. an etchant 2. a drying agent (optional) Third an infiltrant according to claim 1.