WO2015126865A1

WO2015126865A1 - Adhesive bonding composition and use thereof

Info

Publication number: WO2015126865A1
Application number: PCT/US2015/016250
Authority: WO
Inventors: Adrian Eckert; Michael Cub; Bettina Hailand; Ines EDELMANN; Christoph Thalacker; Karsten Dede; Uwe Hoheisel; Reinhold Hecht
Original assignee: 3M Innovative Properties Company
Priority date: 2014-02-18
Filing date: 2015-02-18
Publication date: 2015-08-27
Also published as: CN106029044B; JP2017506242A; US9844493B2; EP3107521A1; CN106029044A; US20170065495A1; EP3107521B1; JP6688737B2

Abstract

An adhesive dental composition comprising apolymerizable monomer (1), a polymerizable monomer (2) comprising an acidic moiety,initiator component(s), filler component(s) in an amount of less than about 15 wt.-%, wt.-% with respect to the whole weight of the composition, the polymerizable monomer (1) being characterized as follows: having exactly two (meth)acrylate reactive moieties, having an unsymmetrical backbone as linkage between the (meth)acrylate reactive moieties, the two (meth)acrylate reactive moieties being attached onto the unsymmetrical monomer backbone as alkyl esters, the unsymmetrical backbone comprising one aromatic moiety of the phenolic type, the polymerizable monomer (1) not containing an acidic moiety, other atoms than carbon, hydrogen, and oxygen, bisphenol moieties. The invention also relates to the use of the adhesive dental composition as dental adhesive, sealant, cement or for bonding or cementing a material to the surface of hard dental tissue.

Description

ADHESIVE BONDING COMPOSITION AND USE THEREOF

Field of the Invention

The invention relates to a storage stable adhesive dental composition which is in particular useful for bonding purposes. The composition comprises a hardenable resin matrix comprising acidic and non-acidic hardenable components, a solvent, a filler and an initiator.

Background Art

Dental adhesive compositions are generally known in the art. Those compositions are typically used for bonding dental restorative compositions to the surface of hard dental tissue, e.g. the surface of a prepared tooth cavity.

Dental adhesive compositions are often light curable and thus contain the respective initiator components. The dental compositions are typically provided to the dental practitioner in an application device, such as a vial.

The instruction of use often requests the dental practitioner to store the dental adhesive composition in a fridge. Otherwise, the storage stability given by the manufacturer cannot be guaranteed.

Dental adhesive compositions typically contain a variety of components, each of which may have an influence on the storage stability.

Sometimes the initiator components contained in the adhesive composition are assumed to be critical for storage stability.

In this respect JP 2006/111584 (Tokuyama) describes a dental curable composition comprising a chemical polymerization initiator system comprising an aryl borate salt, an acid and a monomer having low solubility to the aryl borate salt.

Other efforts are more concentrated on improving the device for storing the adhesive composition. In this respect US 2010/075276 (Shofu) describes a storage container for a dental adhesive, comprising an elongated container portion that can store a liquid therein, wherein one end surface of said container portion has a discharge port communicating with an outside, the other end surface of said container portion is closed by a bottom wall, and a tail portion is formed protruding from said bottom wall to the side opposite from the discharge port.

Other efforts are more concentrated on adjusting the molecular structure of the polymerizable components contained in the adhesive composition.

In this respect WO 2009/027005 (Dentsply) suggests a hydrolysis-stable polymerizable monomers having a particular formula.

In contrast to this US 2010/024683 (Mitsui) is more focusing on the acidic components contained in the dental composition. In this respect a phosphate compound is described comprising an unsaturated double bond represented by a particular formula.

WO 00/69394 (3M) relates to a stable one -part dental material comprising a) resin comprising a mono-acid compound having a molecular weight between about 80-5,000, said compound comprising only one acid functionality and further comprising at least one polymerizable functionality b) a fluoride source containing polyvalent metal ions and c) photopolymerization initiator, said composition being free of a storage stability- deleterious amount of a compound having more than one acid functionality. US 3,853,962 (Gander) relates to dental restorative cements comprising the methacrylate monomer 1,3-bis [2-,3-di(methacryloxy)-propoxy]-benzene. Restorative compositions containing this kind of monomer are said to have improved compressive strength and related physical properties.

US 2003/0167968 (Erdman et al.) relates to dental materials which contain hydrolysis-resistant phosphonic acids with ethylenically unsaturated double bonds and which are especially suitable for use as adhesion promoters.

US 4,539,382 (Omura et al) describes a method of restoring a carious tooth, the method comprising applying to the wall surface of a cavity in a carious tooth an adhesive composition comprising a certain amount of a certain polymerizable monomer, a certain amount of a copolymerizable vinyl monomer and a certain amount of a curing agent, and filling said cavity with a dental filling composition.

US 2011/0315928 Al (Jin at al.) relates to a low viscosity and low stress dental composition comprising at least one low stress polymerizable resin and at least one filler. The dental composition are said to have high depth of cure and self-leveling characteristics and are capable of bulk application.

WO 2012/106083 Al (3M) relates to a dental composition comprising a certain compound (A), a filler (B), and an initiator (C), wherein compound (A) comprises a certain backbone unit and one or two spacer units having a certain structure. Thus, there is still room for improvement especially with regard to the requirements to be fulfilled with respect to modern dental materials.

Dentists still have a demand for long lasting bondings with reliable physical properties. The practitioner in particular is also interested in storage stable compositions.

Adhesive composition described in the prior art, however, are often inferior with respect to storage stability. In particular, it was found that the adhesive strength values often drop over time, i.e. after having stored the composition for a certain period of time.

Description of the Invention

Thus, it is an object of the present invention to provide a more storage stable adhesive dental composition showing a sufficient adhesion even after having stored the composition under severe conditions.

A suitable means to determine storage stability is to measure e.g. the adhesion properties of a composition before and after having stored the composition for a certain period of time. To accelerate this measurement, the compositions are often stored for a reduced period of time but under severe conditions.

To address this object, according to one embodiment the present invention features an adhesive dental composition comprising

- Polymerizable monomer (1),

- Polymerizable monomer (2) comprising an acidic moiety,

- Optionally solvent(s), - Initiator component(s),

- optionally filler component(s) in an amount of less than about 15 wt.-% or less than about 10 wt.-%, wt.-% with respect to the whole weight of the composition,

wherein polymerizable monomer (1) is as described in the claims.

The polymerizable monomer (1) is characterized as follows:

- having exactly two (meth)acrylate reactive moieties,

- having an unsymmetrical backbone as linkage between the (meth)acrylate reactive moieties,

- the two (meth)acrylate reactive moieties being attached onto the unsymmetrical monomer backbone as alkyl esters,

- the unsymmetrical backbone comprising at least one aromatic moiety of the phenolic type,

the polymerizable monomer (1) not containing

- other atoms than carbon, hydrogen, and oxygen,

- other aromatic moieties than aromatic moieties of the phenolic type,

- bisphenol moieties,

the adhesive composition having preferably a pH value of less than about 4, if brought in contact with water Moreover, the invention features a method of using the adhesive dental composition as dental adhesive, sealant, cement or for bonding or cementing a material to the surface of hard dental tissue.

Unless defined differently, for this description the following terms shall have the given meaning:

A "dental composition" or a "composition for dental use" or a "composition to be used in the dental field" is any composition which can and is to be used in the dental field. In this respect the composition should not be detrimental to the patients' health and thus free of hazardous and toxic components being able to migrate out of the composition. Examples of dental compositions include dental adhesives or dental bonding agents. Dental compositions are typically hardenable compositions. Dental compositions for hardening in the mouth can be hardened at ambient conditions, including a temperature range from about 15 to 50°C or from about 20 to 40°C within a time frame of about 30 min or 20 min or 10 min. Higher temperatures are not recommended as they might cause pain to the patient and may be detrimental to the patient^'s health. Dental compositions are typically provided to the practitioner in comparable small volumes, that is volumes in the range from about 0.1 to about 100 ml or from about 0.5 to about 50 ml or from about 1 to about 30 ml. Thus, the storage volume of useful packaging devices is typically within these ranges. As used herein "adhesive" or "dental adhesive" refers to a composition used as a pre-treatment on a dental structure (e. g., a tooth) to adhere a "dental material" (e. g., "restorative" an orthodontic appliance (e. g., bracket), or an "orthodontic adhesive") to a dental surface. An "orthodontic adhesive" refers to a composition used to adhere an orthodontic appliance to a dental (e. g., tooth) surface. Generally, the dental surface is pre- treated, e. g., by etching, priming, and/or applying an adhesive to enhance the adhesion of the "orthodontic adhesive" to the dental surface.

An "initiator system" or "initiator" shall include those components of the dental composition being able to start or initiate the curing process of the hardenable components, also described herein as "curing the hardenable components." A "resin matrix" shall mean the organic part of the dental composition being composed of the hardenable components and organic diluents, if present.

A "hardenable component or material" (e.g., "polymerizable component" or "crosslinkable component") is any component which can be cured or solidified e.g., by heating to cause polymerization, chemical crosslinking, radiation-induced polymerization or crosslinking by using a redox initiator. A hardenable component may contain, for example, only one, two, three or more polymerizable groups. Typical examples of polymerizable groups include unsaturated carbon groups, such as a vinyl group being present e.g. in a (meth)acrylate group.

A "curable composition" is a mixture of two or more components, the mixture being able to be cured or solidified e.g., by heating to cause chemical crosslinking, radiation-induced polymerization or crosslinking by using a redox initiator. A curable composition may advantageously include a hardenable component.

A "monomer" is any chemical substance which can be characterized by a chemical formula, bearing one or more polymerizable groups (including (meth)acrylate groups) which can be polymerized to oligomers or polymers thereby increasing the molecular weight. The molecular weight of monomers can usually simply be calculated based on the chemical formula given.

As used herein, "(meth)acryl" is a shorthand term referring to "acryl" and/or "methacryl". For example, a "(meth) acryloxy" group is a shorthand term referring to either an acryloxy group (i. e.,CH2=CH-C(0)-0-) and/or a methacryloxy group (i. e., CH2=C(CH3)-C(0)-0-). Similarly, (meth)acrylate is a shorthand term referring to "acrylate" and/or "methacrylate."

"Curing," "hardening," and "setting reaction" are used interchangeably and refer to a reaction wherein physical properties such as viscosity and hardness of a composition change (e.g., increase) over time due to a chemical reaction between the individual components.

A "polymerizable monomer(s) with acidic moiety(s)" is meant to include monomers, oligomers, and polymers having ethylenic unsaturation and acid and/or acid- precursor functionality. Acidic-precursor functionalities include, e.g. anhydrides, acid halides and pyrophosphates. The acidic group preferably comprises one or more carboxylic acid residues, such as -COOH or -CO-0-CO-, phosphoric acid residues, such as -0-P(0)(OH)OH, phosphonic acid residues such as C-P(0)(OH)OH, sulfonic acid residues, such as -SO3H or sulfuric acid residues such as -SO2H.

A "phenolic type" moiety is generally understood as an aromatic moiety bearing at least one oxygen atom directly attached onto an aromatic residue, more precisely, a moiety comprising the structural element [C6RxO] with x being 1, 2, 3, 4, 5 or 6, R being H, alkyl (e.g. CI to C8), -0-, -CO- or -C(0)0- and C6 forming an aromatic ring. For example, "C6H50-" (phenoxy) represents the most simple "phenolic type" moiety.

A "powder" means a dry, bulk solid composed of a large number of very fine particles that may, for example, flow freely when shaken or tilted. A "particle" means a substance being a solid having a shape which can be geometrically determined. Particles can typically be analysed with respect to e.g. particle size or diameter. Particles may be amorphous or crystalline.

"Storage stable" shall mean that the composition can be stored for at least about 1, 2, 3 or 4 month(s) at about 50°C and atmospheric pressure and still showing sufficient adhesion to dental hard tissue, in particular without showing a reduction of not more than about 80% of the initial adhesive strength in particular with respect to enamel.

"Radiation curable" shall mean that the component (or composition, as the case may be) can be cured by applying radiation, preferably electromagnetic radiation with a wavelength in the visible light spectrum under ambient conditions and within a reasonable time frame (e.g. within about 15, 10 or 5 min).

The term "visible light" is used to refer to light having a wavelength of about 400 to about 700 nanometers (nm).

"Hard dental tissue" means dentin and enamel. "Ambient conditions" mean the conditions which the inventive composition is usually subjected to during storage and handling. Ambient conditions may, for example, be a pressure of about 900 to about 1100 mbar, a temperature of about -10 to about 60 °C and a relative humidity of about 10 to about 100 %. In the laboratory ambient conditions can be adjusted to about 23 °C and about 1013 mbar and about 50% relative humidity. In the dental and orthodontic field ambient conditions are reasonably understood as a pressure of about 950 to about 1050 mbar, temperature of about 15 to about 40 °C and relative humidity of about 20 to about 80%.

A composition is "essentially or substantially free of a certain component within the meaning of the invention, if the composition does not contain said component as an essential feature. Thus, said component is not wilfully added to the composition either as such or in combination with other components or ingredient of other components. A composition being essentially free of a certain component usually contains the component in an amount of less than about 1 wt.-% or less than about 0.1 wt.-% or less than about 0.01 wt.-%> with respect to the whole composition. Ideally, the composition or solution does not contain the said component at all. However, sometimes the presence of a small amount of the said component is not avoidable e.g. due to impurities.

As used herein, "a", "an", "the", "at least one" and "one or more" are used interchangeably. The terms "comprises" or "contains" and variations thereof do not have a limiting meaning where these terms appear in the description and claims. The term "comprising" also includes the more limited expressions "consisting essentially of and "consisting of.

Also herein, the recitations of numerical ranges by endpoints include all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Adding an "(s)" to a term means that the term should include the singular and plural form. E.g. the term "additive(s)" means one additive and more additives (e.g. 2, 3, 4, etc.).

Unless otherwise indicated, all numbers expressing quantities of ingredients, measurement of physical properties such as described below and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about."

Detailed Description of the Invention

It has been found that the adhesive composition described in the present text is superior with respect to a variety of properties:

The compositions described in the present text are sufficient storage stable and show adequate adhesive properties (to enamel and/or dentin) even after having stored the composition under severe conditions.

It further allows the formulation of a composition without the need to use bis- phenol based monomers like Bis-GMA.

Surprisingly it has been found that in particular using curable components or monomers which are non symmetric are suitable to solve the above object.

In certain embodiments the adhesive dental composition fulfils at least one or more, sometimes all of the following features before hardening: - Viscosity: from about 0.05 to about 5 Pa*s or from about 0.1 to about 2 Pa*s measured at 23°C with a shear rate of 100 1/s;

- pH value if brought in contact with water: about 0 to about 3;

- radiation curing;

- storage stable;

- being provided as a one-component mixture.

If desired and more precisely, the viscosity can be determined under the following conditions: 23°C; shear rate: 100 1/s; measured with a cone/plate geometry CP25-1 with a Physica MCR 301 Rheometer, Anton Paar GmbH, Graz, Austria.

If dissolved or dispersed in water (e.g. 1 g in 10 ml) the composition typically exhibits a pH value in the range from about 0 to about 4 or from about 1 to about 3. That is, the composition as a whole is acidic. If desired the pH value can be determined with a pH electrode or by using a pH sensitive paper. The invention provides a composition which can be hardened in an acceptable time frame, e.g., less than about 300 seconds (s) or less than about 180 s or less than about 120 s, and to a sufficient depth using visible light source equipment already available in the dental office.

In certain embodiments the adhesive dental composition fulfils at least one or more, sometimes all of the following features after hardening: adhesion to dentin (Adl) determined according to ISO 29022:2013 of a freshly prepared dental composition: at least about 25 MPa or at least about 29 or at least about 33 MPa; - adhesion to enamel (Adl) determined according to wire ISO 29022:2013 of a freshly prepared dental composition: at least about 18 MPa or at least about 21 or at least about 24 MPa; adhesion to dentin (Ad2) determined according to ISO 29022:2013 of a dental composition that was stored for four months at a temperature of 50 °C: at least about 12 MPa or at least about 16 or at least about 20 MPa; adhesion to enamel (Ad2) determined according to wire ISO 29022:2013 of a dental composition that was stored for four months at a temperature of 50 °C: at least about 5 MPa or at least about 7 or at least about 9 MPa.

"Freshly prepared" means that the composition is used without delay after preparation (e.g. within about 5 days of storage at room temperature).

The polymerizable monomer (1) is one component of the hardenable resin matrix contained in the dental adhesive composition.

The polymerizable monomer (1) can be described as follows:

- having exactly two (meth)acrylate reactive moieties,

- the unsymmetrical backbone comprising exactly one aromatic moiety of the phenolic type,

- preferably containing not more than one additional aromatic moiety within the unsymmetrical monomer backbone not being part of the linkage between the reactive groups but being attached onto this linkage between the reactive groups,

- preferably having exactly two (meth)acrylate reactive groups that are always attached onto the unsymmetrical monomer backbone as alkyl esters,

the polymerizable monomer (1) not containing

- other atoms than carbon, hydrogen, and oxygen,

- other aromatic moieties than aromatic moieties of the phenolic type,

- bisphenol moieties.

- optionally other oxygen based linkages than ethers and esters.

The polymerizable monomer (1) can also be characterized by the following features:

- having a molecular weight of about 300 to about 600;

- not solidifying at room temperature. According to one embodiment, the adhesive composition typically has a pH value of less than about 4 or less than about 3, if brought in contact with water.

The molecular weight of the polymerizable monomer (1) is comparably low. This can be beneficial for formulating low viscous compositions, which can more easily wet the surface of hard dental tissue and is able to migrate into the pores of a hard dental tissue surface.

More precisely, the polymerizable monomer (1) is characterized by the following formula (I):

with:

B-0-A-[-0-B'-]a representing the unsymmetrical monomer backbone as linkage between the reactive groups,

a = 0 or 1 ,

A being selected from the following moieties:

A being always attached as aryl-alkyl ether onto B and / or B',

B being selected from the following moieties: *- CH₂)b-* , *-(CH2-CH₂-0-CH2-CH₂)-* , *-(CH₂-CH2-0-CH2-CH2-CH₂)-* , *-(CH₂-

B being always attached as alkyl ester onto the (meth)acrylate reactive moiety,

b = 2 to 6,

B' being selected from *-(CH2 --* , *-(CH2-CH₂-0-CH2-CH₂)-* ,

B' being always attached as alkyl ester onto the (meth)acrylate reactive moiety, b' = 2 to 6,

R = H, methyl,

X being selected from H, methyl, ethyl, hexyl, tert-butyl,

"*" representing those sites of a moiety of the monomer, where that moiety is bonded to another moiety of the monomer.

According to a further embodiment the polymerizable monomer (1) can be characterized by either of formula (la) or formula (lb):

with:

B-O-A-O-B' being an unsymmetrical monomer backbone as linkage between the reactive moieties,

A bein selected from the moieties:

A being always attached as aryl-alkyl ether onto B and B',

B being selected from the moieties: *-(CH₂)b-* , *-(CH₂-CH₂-0-CH₂-CH₂)-* , *-(CH₂-CH₂-0-CH₂-CH₂-CH₂)-* , *-(CH₂-

CH₂-CH₂-0-CH₂-CH₂-CH₂₎_* ,

B being always attached as alkyl ester onto the (meth)acrylate reactive moiety, b = 2 to 6,

B' being selected from the moieties:

*-(CH₂)_b-* , *-(CH₂-CH₂-0-CH₂-CH₂)-* , *-(CH₂-CH₂-0-CH₂-CH₂-CH₂)-* , *-(CH₂-

CH₂-CH₂-0-CH₂-CH₂-CH₂₎_* ,

R = H, methyl,

X = H, methyl, ethyl, hexyl, tert-butyl;

or

with:

B-O-A being an unsymmetrical monomer backbone as linkage between the reactive moieties,

A being selected from the moieties:

A being always attached as aryl-alkyl ether onto B and always attached as alkyl ester onto the (meth)acrylate reactive moiety,

B being selected from: *-(CH₂)b-* , *-(CH₂-CH₂-0-CH₂-CH₂)-* , ^"

,

R = H, methyl;

Specific examples of for the polymerizable monomer (1) include:

-15-

-16-

In all the above formulas R can independently be selected from H and CH3, meaning that in each component R can be either methyl or hydrogen, or that one R is methyl and the other R is hydrogen.

The polymerizable monomers (1) described in the present text can be synthesized e.g. as described in the example section below.

When doing so, the skilled person will realize that depending on the polymerizable monomer (1) during synthesis a single non- symmetrical compound is obtained as well as a mixture containing different non-symmetrical components or a mixture containing minor symmetrical components besides the major non-symmetrical compound is obtained. For a polymerizable monomer (1) containing a non- symmetrical backbone based on a non-symmetrically substituted aromatic moiety, the synthesis will result either in a single non-symmetrical compound or in a composition containing 100 mol-% of nonsymmetrical components. For a polymerizable monomer (1) containing a non- symmetrical backbone based on a symmetrically substituted aromatic moiety and unless the composition is further purified, the synthesis will usually result due to statistics in a composition containing 50 mol-% of the non-symmetrical compound as the major component besides 25 mol-% each of symmetrical compounds as minor components.

Mixtures of two, three or more of the polymerizable monomers (1) can be used, if desired.

The polymerizable monomer (1) is typically present in the following amounts:

- Lower limit: at least about 5 or at least about 10 or at least about 15 wt.-%;

- Upper Limit: up to about 85 or up to about 80 or up to about 70 wt.-%;

- Range: from about 5 to about 85 or from about 10 to about 80 or from about 15 to about 70 wt.-%,

wt.-% with respect to the amount of the whole composition.

Polymerizable Monomer (2) with acidic moiety

The polymerizable monomer (2) forms a further component of the hardenable resin matrix.

The adhesive composition described in the present text further comprises a polymerizable monomer (2) with an acidic moiety. The nature and structure of polymerizable monomer (2) is not particularly limited, either unless the desired result cannot be achieved.

The presence of polymerizable monomer (3) is beneficial because it provides the composition with the required acidity.

The polymerizable components with acid moiety (Al) can typically be represented by the following formula

with A being an ethylenically unsaturated group, such as a (meth)acryl moiety,

B being a spacer group, such as (i) linear or branched CI to C12 alkyl, optionally substituted with other functional groups (e.g. halogenides (including CI, Br, I), OH or mixtures thereof) (ii) C6 to C12 aryl, optionally substituted with other functional groups (e.g. halogenides, OH or mixtures thereof), (iii) organic group having 4 to 20 carbon atoms bonded to one another by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl and/or sulfonyl linkages,and C being an acidic group, m, n being independently selected from 1, 2, 3, 4, 5 or 6, wherein the acidic group comprises one or more carboxylic acid residues, such as -COOH or -CO-0-CO-, phosphoric acid residues, such as -0-P(0)(OH)OH, phosphonic acid residues, such as C-P(0)(OH)(OH), sulphonic acid residues, such as -SO3H or sulfuric acid residues such as -SO2H.

Examples of polymerizable components with acid moiety include, but are not limited to glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl (meth)acrylate (e.g., HEMA) phosphate, bis((meth)acryloxyethyl) phosphate, (meth)acryloxypropyl phosphate, bis((meth)acryloxypropyl) phosphate, bis((meth)acryloxy)propyloxy phosphate, (meth)acryloxyhexyl phosphate, bis((meth)acryloxyhexyl) phosphate, (meth)acryloxyoctyl phosphate, bis((meth)acryloxyoctyl) phosphate, (meth)acryloxydecyl phosphate, bis((meth)acryloxydecyl) phosphate, caprolactone methacrylate phosphate, citric acid di- or tri-methacrylate, poly(meth)acrylated oligomaleic acid, poly(meth)acrylated polymaleic acid, poly(meth)acrylated poly(meth)acrylic acid, poly(meth)acrylated polycarboxyl- polyphosphonic acid, poly(meth)acrylated polychlorophosphoric acid, poly(meth)acrylated polysulfonate, poly(meth)acrylated polyboric acid, and the like. Derivatives of these hardenable components bearing an acid moiety that can readily react e.g. with water to form the specific examples mentioned above, like acid halides or anhydrides are also contemplated.

Also monomers, oligomers, and polymers of unsaturated carboxylic acids such as (meth)acrylic acids, aromatic (meth)acrylated acids (e.g., methacrylated trimellitic acids), and anhydrides thereof can be used.

Some of these compounds can be obtained, e.g., as reaction products between isocyanatoalkyl (meth)acrylates and carboxylic acids. Additional compounds of this type having both acid-functional and ethylenically unsaturated components are described in US 4,872,936 (Engelbrecht) and US 5,130,347 (Mitra). A wide variety of such compounds containing both the ethylenically unsaturated and acid moieties can be used. If desired, mixtures of such compounds can be used. Using (meth)acrylate functionalized polyalkenoic acids is often preferred as those components were found to be useful to improve properties like adhesion to hard dental tissue, formation of a homogeneous layer, viscosity, or moisture tolerance.

According to one embodiment, the composition contains (meth)acrylate functionalized polyalkenoic acids, for example, AA:ITA:IEM (copolymer of acrylic acid:itaconic acid with pendent methacrylates) .

These components can be made by reacting e.g. an AA:ITA copolymer with 2- isocyanatoethyl methacrylate to convert at least a portion of the acid groups of the copolymer to pendent methacrylate groups. Processes for the production of these components are described, e.g., in Example 11 of US 5,130,347 (Mitra)); and those recited in US 4,259,075 (Yamauchi et al), US 4,499,251 (Omura et al), US 4,537,940 (Omura et al), US 4,539,382 (Omura et al), US 5,530,038 (Yamamoto et al), US 6,458,868 (Okada et al), and EP 0 712 622 Al (Tokuyama Corp.) and EP 1 051 961 Al (Kuraray Co., Ltd.).

Mixtures of two, three or more of the polymerizable monomers (2) can be used, if desired.

The polymerizable monomer (2) is typically present in the following amounts:

- Lower limit: at least about 1 or at least about 5 or at least about 10 wt.-%

- Upper Limit: up to about 80 or up to about 70 or up to about 60 wt.-%

- Range: from about 1 to about 80 or from about 5 to about 70 or from about 10 to about 60 wt.-%,

wt.-% with respect to the amount of the whole composition.

The adhesive composition described in the present text may optionally also comprise a polymerizable monomer (3) without an acidic moiety.

The polymerizable monomer (3) may form a further component of the hardenable resin matrix. The nature and structure of polymerizable monomer (3) is not particularly limited, either unless the desired result cannot be achieved.

The resin matrix may also comprise one or more hardenable component(s) without an acid moiety as component (A2). This component is typically a free-radically polymerizable material, including ethylenically unsaturated monomer, monomers or oligomers or polymers.

Suitable polymerizable components without an acidic moiety can be characterized by the following formula:

with A being an ethylenically unsaturated group, such as a (meth)acryl moiety,

B being selected from (i) linear or branched CI to C12 alkyl, optionally substituted with other functional groups (e.g. halogenides (including CI, Br, I), OH or mixtures thereof) (ii) C6 to C12 aryl, optionally substituted with other functional groups (e.g. halogenides, OH or mixtures thereof), or (iii) organic group having 4 to 20 carbon atoms bonded to one another by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl and/or sulfonyl linkages, m, n being independently selected from 0, 1, 2, 3, 4, 5 or 6 with the proviso that n+m is greater 0, that is that at least one A group is present.

Such polymerizable materials include mono-, di- or poly-acrylates and methacrylates such as methyl acrylate, methyl methacrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate, glycerol di(meth)acrylate, the diurethane dimethacrylate called UDMA (mixture of isomers, e.g. Rohm Plex 6661-0) being the reaction product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate (TMDI), glycerol tri(meth)acrylate, ethyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate, triethyleneglycol di(meth)acrylate, 1,3-propanediol diacrylate, 1,3 -propanediol dimethacrylate, 1,6 hexandiol di(meth)acrylate, 1,10 decanediol di(meth)acrylate, 1,12 dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1 ,4-cyclohexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexa(meth)acrylate, bis[l-(2-(meth)acryloxy)]-p-ethoxyphenyldimethylmethane, and trishydroxyethyl-isocyanurate trimethacrylate; the bis-acrylates and bis-methacrylates of polyethylene glycols of molecular weight 200-500, copolymerizable mixtures of acrylated monomers (see e.g. US 4,652,274), and acrylated oligomers (see e.g. US 4,642,126); and vinyl compounds such as styrene, divinyl succinate, divinyl adipate and divinylphthalate; polyfunctional (meth)acrylates comprising urethane, urea or amide groups. Mixtures of two or more of these free radically polymerizable materials can be used, if desired.

These ethylenically unsaturated monomers can be employed in the dental composition(s) either alone or in combination with other ethylenically unsaturated monomers.

Monomers comprising a hydroxyl moiety can also be added. Suitable compounds include 2-hydroxyethyl (meth)acrylate (HEMA), 2- or 3-hydroxypropyl (meth)acrylate, 4- hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, dialkylene glycol mono(meth)acrylate, for example, diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and further 1,2- or 1,3- and 2,3-dihydroxypropyl (meth)acrylate, 2- hydroxypropyl- 1 ,3-di(meth)acrylate, 3-hydroxypropyl- 1 ,2-di(meth)acrylate, N- (meth)acryloyl-l,2-dihydroxypropylamine, N-(meth)acryloyl-l,3-dihydroxypropylamine, adducts of phenol and glycidyl (meth)acrylate, for example, l-phenoxy-2-hydroxypropyl (meth)acrylate, l-naphthoxy-2-hydroxypropyl (meth)acrylate, bisphenol A diglycidyl (meth)acrylate and the like, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and 2,3-dihydroxypropyl (meth)acrylate are particularly preferable. If desired, mixtures of one or more of these components can be used.

In addition or besides those components, other hardenable components which can be added include oligomeric or polymeric compounds, such as polyester urethane (meth)acrylates, polyether urethane (meth)acrylates, polycarbonate urethane (meth)acrylates and poly(meth)acrylate urethane (meth)acrylates. The molecular weight of these compounds is typically less than 20,000 g/mol, particularly less than 15,000 g/mol and in particular less than 10,000 g/mol. Adding these components may be used to adjust the rheological properties.

Mixtures of two, three or more of the polymerizable monomers (3) can be used, if desired.

The polymerizable monomer (3) is typically present in the following amounts:

- Lower limit: at least about 0 or at least about 1 or at least about 5 wt.-%

- Upper Limit: up to about 70 or up to about 60 or up to about 50 wt.-%

- Range: from about 0 to about 70 or from about 1 to about 60 or from about 5 to about 50 wt.-%,

wt.-% with respect to the amount of the whole composition.

The adhesive composition described in the present text may also comprise a solvent.

If desired, any solvent may be used which does not react appreciably with the other components of the composition. Adding a solvent can be beneficial for adjusting the viscosity of the composition. If the composition is to be used as a dental adhesive, the composition typically contains a solvent.

Examples of solvents include, but are not limited to water, linear, branched or cyclic, saturated or unsaturated alcohols, ketones, esters or mixtures of two or more of said type of solvents with 2 to IO C atoms or mixtures thereof. Preferred alcoholic solvents include methanol, ethanol, iso-propanol and n-propanol.

Other suitable organic solvents are THF, acetone, methylethyl ketone, cyclohexanol, toluene, alkanes and acetic acid alkyl esters, in particular acetic acid ethyl ester. If desired, the solvent can be present in the following amounts:

- Lower limit: at least 0 or at least about 1 or at least about 5 wt.-%

- Upper Limit: up to about 40 or up to about 30 or up to about 20 wt.-%

- Range: from about 0 to about 40 or from about 1 to about 30 or from about 5 to about 20 wt.-%,

wt.-% with respect to the amount of the whole composition. The adhesive composition described in the present text also comprises an initiator. If more than one initiator component is required, the initiator is also referred to as initiator system. The nature of the initiator is not particularly limited, unless the desired result cannot be achieved.

The initiator system can comprise systems which are capable of initiating polymerization via radiation, heat or a combination of both.

A class of initiators capable of initiating polymerization of the hardenable components of the resin matrix which contain free radically active functional groups includes free radical-generating photoinitiators, optionally combined with a photosensitizer or accelerator.

Such initiators typically can be capable of generating free radicals for addition polymerization upon exposure to light energy having a wavelength between about 200 and about 700 nm.

Initiator components which can undergo an alpha-cleavage are sometimes preferred.

Using acylphosphine oxides as initiators or part of the initiator system was found to be particularly useful. Suitable acylphosphine oxides can be characterized by the following formula

(R⁹)₂— P(=0)— C(=0)— R¹⁰

wherein each R⁹ individually can be a hydrocarbyl group such as alkyl, cycloalkyl, aryl, and aralkyl, any of which can be substituted with a halo-, alkyl- or alkoxy-group, or the two R⁹ groups can be joined to form a ring along with the phosphorous atom, and wherein R¹⁰ is a hydrocarbyl group, an S-, 0-, or N-containing five- or six-membered heterocyclic group, or a -Z-C(=0)-P(=0)- (R⁹)2 group, wherein Z represents a divalent hydrocarbyl group such as alkylene or phenylene having from 2 to 6 carbon atoms.

Suitable systems are also described e.g. in US 4,737,593, the content of which is herewith incorporated by reference. Preferred acylphosphine oxides useful in the invention are those in which the R⁹ and R¹⁰ groups are phenyl or lower alkyl- or lower alkoxy-substituted phenyl. By "lower alkyl" and "lower alkoxy" is meant such groups having from 1 to 4 carbon atoms. Most preferably, the acylphosphine oxide is 2,4,6-trimethylbenzoyl diphenyl phosphine oxide (Lucirin™ TPO, BASF).

Suitable bisacylphosphine oxides can also be described by the following formula

wherein n is 1 or 2, and R⁴, R⁵, R⁶ and R⁷ are H, CI -4 alkyl, CI -4 alkoxyl, F, CI or Br; R² and R³, which are the same or different, stand for a cyclohexyl, cyclopentyl, phenyl, naphthyl, or biphenylyl radical, a cyclopentyl, cyclohexyl, phenyl, naphthyl, or biphenylyl radical substituted by F, CI, Br, I, CI -4 alkyl and/or CI -4 alkoxyl, or an S or N-containing 5-membered or 6-membered heterocyclic ring; or R² and R³ are joined to form a ring containing from 4 to 10 carbon atoms and being optionally substituted by 1 to 6 C 1-4 alkyl radicals. More specific examples include: bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)- 4-ethoxyphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-biphenylylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2- naphthylphosphine oxide, bis-(2,6-dichlorobenzoyl)-l-napthylphosphine oxide, bis-(2,6- dichlorobenzoyl)-4-chlorophenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,4- dimethoxyphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)decylphosphine oxide, bis- (2,6-dichlorobenzoyl)-4-octylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5- dimethylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichloro-3,4,5- trimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichloro-3,4,5- trimethoxybenzoyl)-4-ethoxyphenylphosphine oxide, bis-(2 -methyl- 1 -naphthoyl)-2,5- dimethylphenylphosphine oxide, bis-(2-methyl-l-naphthoyl)phenylphosphine oxide, bis- (2 -methyl- 1 -naphthoyl)-4-biphenylylphosphine oxide, bis-(2 -methyl- 1 -naphthoyl)-4- ethoxyphenylphosphine oxide, bis-(2-methyl-l-naphthoyl)-2-naphthylphosphine oxide, bis-(2 -methyl- 1 -naphthoyl)-4-propylphenylphosphine oxide, bis-(2 -methyl- 1 -naphthoyl)- 2,5-dimethylphosphine oxide, bis-(2-methoxy- 1 -naphthoyl)-4-ethoxyphenylphosphine oxide, bis-(2-methoxy-l-naphthoyl)-4-biphenylylphosphine oxide, bis-(2-methoxy-l- naphthoyl)-2-naphthylphosphine oxide and bis-(2-chloro-l-naphthoyl)-2,5- dimethylphenylphosphine oxide.

The acylphosphine oxide bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide (IRGACURE™ 819, Ciba Specialty Chemicals, Tarrytown, NY) is sometimes preferred.

Tertiary amine reducing agents may be used in combination with an acylphosphine oxide. Illustrative tertiary amines useful in the invention include ethyl 4-(N,N-dimethyl- amino)benzoate (EDMAB) and Ν,Ν-dimethylaminoethyl methacrylate (DMAEMA).

Commercially-available phosphine oxide photoinitiators capable of free-radical initiation when irradiated at wavelengths of greater than 400 nm to 1200 nm include a 25:75 mixture, by weight, of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide and 2-hydroxy-2-methyl-l-phenylpropan-l-one (IRGACURE™ 1700, Ciba Specialty Chemicals), 2-benzyl-2-(N,N-dimethylamino)-l-(4-morpholinophenyl)-l- butanone (IRGACURE™ 369, Ciba Specialty Chemicals), bis^5-2,4-cyclopentadien-l- yl)-bis(2,6-difluoro-3-(lH-pyrrol-l-yl)phenyl) titanium (IRGACURE™ 784 DC, Ciba Specialty Chemicals), a 1 : 1 mixture, by weight, of bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide and 2-hydroxy-2-methyl-l-phenylpropane-l-one (DAROCUR™ 4265, Ciba Specialty Chemicals), and ethyl-2,4,6-trimethylbenzylphenyl phosphinate (LUCIRIN™ LR8893X, BASF Corp., Charlotte, NC).

A variety of visible or near-IR photoinitiator systems may also be used for photopolymerization of free-radically polymerizable materials. For example, a photoinitiation system can be used selected from systems which initiate polymerization via a two component system of an amine and an a-diketone. Such systems are described e.g. in US 4,071,424 and WO 2009151957, which are herein incorporated by reference. Alternatively, the resin can be combined with a three components or ternary photoinitiator system. Suitable systems are described in US 5,545,676 and WO 2009151957, which are incorporated herein by reference.

In the ternary photoinitator system, the first component is an iodonium salt, i.e., a diaryliodonium salt. The iodonium salt is preferably soluble in the monomer and shelf- stable (i e., does not spontaneously promote polymerization) when dissolved therein in the presence of the sensitizer and donor. Accordingly, selection of a particular iodonium salt may depend to some extent upon the particular monomer, polymer or oligomer, sensitizer and donor chosen. Suitable iodonium salts are described in US 3,729,313, US 3,741,769, US 3,808,006, US 4,250,053 and US 4,394,403, the iodonium salt disclosures of which are incorporated herein by reference. The iodonium salt can be a simple salt (e.g., containing an anion such as CI^", Br^", Γ or C4H5 SO3^") or a metal complex salt (e.g., containing SbFsOH^" or AsF₆ ^"). Mixtures of iodonium salts can be used if desired. Preferred iodonium salts include diphenyliodonium salts such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate and diphenyliodonium tetrafluoroborate. The second component in a ternary photoinitiator system is a sensitizer. The sensitizer desirably is soluble in the monomer, and is capable of light absorption somewhere within the range of wavelengths of greater than 400 to 1200 nanometers, more preferably greater than 400 to 700 nanometers and most preferably greater than 400 to about 600 nanometers. The sensitizer may also be capable of sensitizing 2-methyl-4,6- bis(trichloromethyl)-s-triazine, using the test procedure described in US 3,729,313, which is incorporated herein by reference. Preferably, in addition to passing this test, a sensitizer is also selected based in part upon shelf stability considerations. Accordingly, selection of a particular sensitizer may depend to some extent upon the particular monomer, oligomer or polymer, iodonium salt and donor chosen. Suitable sensitizers can include compounds in the following categories: ketones, coumarin dyes (e.g., ketocoumarins), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotriaryl methanes, merocyanines, squarylium dyes and pyridinium dyes. Ketones (e.g., monoketones or alpha-diketones), ketocoumarins, aminoarylketones and p-substituted aminostyryl ketone compounds are preferred sensitizers. For applications requiring high sensitivity, it is preferred to employ a sensitizer containing a julolidinyl moiety. For applications requiring deep cure (e.g., cure of highly-filled composites), it is preferred to employ sensitizers having an extinction coefficient below about 1000, more preferably below about 100, at the desired wavelength of irradiation for photopolymerization. Alternatively, dyes that exhibit reduction in light absorption at the excitation wavelength upon irradiation can be used.

For example, a preferred class of ketone sensitizers has the formula: ACO(X)b B, where X is CO or CR⁵ R⁶, where R⁵ and R⁶ can be the same or different, and can be hydrogen, alkyl, alkaryl or aralkyl, b is zero or one, and A and B can be the same or different substituted (having one or more non-interfering substituents) or unsubstituted aryl, alkyl, alkaryl, or aralkyl groups, or together A and B can form a cyclic structure which can be a substituted or unsubstituted cycloaliphatic, aromatic, heteroaromatic or fused aromatic ring.

Suitable ketones of the above formula include monoketones (b=0) such as 2,2-, 4,4- or 2,4-dihydroxybenzophenone, di-2-pyridyl ketone, di-2-furanyl ketone, di-2- thiophenyl ketone, benzoin, fluorenone, chalcone, Michler's ketone, 2-fluoro-9- fluorenone, 2-chlorothioxanthone, acetophenone, benzophenone, 1- or 2-acetonaphthone, 9-acetylanthracene, 2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenyl, propiophenone, n- butyrophenone, valerophenone, 2-, 3- or 4-acetylpyridine, 3-acetylcoumarin and the like. Suitable diketones include aralkyldiketones such as anthraquinone, phenanthrenequinone, 0-, m- and p-diacetylbenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7- and 1,8-diacetylnaphthalene, 1,5-, 1,8- and 9,10-diacetylanthracene, and the like. Suitable alpha-diketones (b=l and X=CO) include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3- heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzil, 2,2'- 3 3'- and 4,4'-dihydroxylbenzil, furil, di-3,3'-indolylethanedione, 2,3-bornanedione (camphorquinone), biacetyl, 1 ,2-cyclohexanedione, 1 ,2-naphthaquinone, acenaphthaquinone, and the like. The third component of a ternary initiator system is a donor. Preferred donors include, for example, amines (including aminoaldehydes and aminosilanes), amides (including phosphoramides), ethers (including thioethers), ureas (including thioureas), ferrocene, sulfuric acids and their salts, salts of ferrocyanide, ascorbic acid and its salts, dithiocarbamic acid and its salts, salts of xanthates, salts of ethylene diamine tetraacetic acid and salts of tetraphenylboronic acid. The donor can be unsubstituted or substituted with one or more non-interfering substituents. Particularly preferred donors contain an electron donor atom such as a nitrogen, oxygen, phosphorus, or sulfur atom, and an abstractable hydrogen atom bonded to a carbon or silicon atom alpha to the electron donor atom. A wide variety of donors is disclosed in US 5,545,676, which is incorporated herein by reference.

Another free-radical initiator system that can alternatively be used in the dental compositions described in the present text is the class of ionic dye counterion complex initiators comprising a borate anion and a complementary cationic dye.

Borate salt photoinitiators are described, for example, in US 4,772,530, US 4,954,414, US 4,874,450, US 5,055,372, and US 5,057,393, the disclosures of which are incorporated herein by reference.

Borate anions useful in these photointiators generally can be of the formula R^R^P^B , wherein R¹, R², R³, and R⁴ independently can be alkyl, aryl, alkaryl, allyl, aralkyl, alkenyl, alkynyl, alicyclic and saturated or unsaturated heterocyclic groups. Preferably, R², R³, and R⁴ are aryl groups and more preferably phenyl groups, and R¹ is an alkyl group and more preferably a secondary alkyl group.

Cationic counterions can be cationic dyes, quaternary ammonium groups, transition metal coordination complexes, and the like. Cationic dyes useful as counterions can be cationic methine, polymethine, triarylmethine, indoline, thiazine, xanthene, oxazine or acridine dyes. More specifically, the dyes may be cationic cyanine, carbocyanine, hemicyanine, rhodamine, and azomethine dyes. Specific examples of useful cationic dyes include Methylene Blue, Safranine O, and Malachite Green. Quaternary ammonium groups useful as counterions can be trimethylcetylammonium, cetylpyridinium, and tetramethylammonium. Other organophilic cations can include pyridinium, phosphonium, and sulfonium.

Photosensitive transition metal coordination complexes that may be used include complexes of cobalt, ruthenium, osmium, zinc, iron, and iridium with ligands such as pyridine, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine, 1,10-phenanthroline, 3,4,7,8- tetramethylphenanthroline, 2,4,6-tri(2-pyridyl-s-triazine) and related ligands.

In a further alternative, heat may be used to initiate the hardening, or polymerization, of free radically active groups. Examples of heat sources suitable for the dental materials described in the present text include inductive, convective, and radiant. Thermal sources should be capable of generating temperatures of at least 40°C to 15°C. This procedure is sometime preferred for initiating polymerization of materials occurring outside of the oral environment.

Yet another alternative class of initiators capable of initiating polymerization of free radically active functional groups that are useful for the dental materials as described in the present text are those that include free radical-generating thermal initiators. Examples include peroxides such as, for example, benzoyl peroxide and lauryl peroxide, and azo compounds such as, for example, 2,2-azobis-isobutyronitrile (AIBN).

If the color of the cured composition matters, an initiator system which does not lead to undesired discoloration should be used. It was found that an initiator system comprising the following components is particularly useful: monoacylphosphine oxides and / or bisacylphosphine oxides.

The initiator system (including the respective initiator component(s)) is typically present in the following amounts:

Lower limit: at least about 0.1 or at least about 0.2 or at least about 0.3 wt.-%;

- Upper limit: utmost about 10 or utmost about 8 or utmost about 6 wt.-%;

Range: from about 0.1 to about 10 or from about 0.2 to about 8 wt.-% or from about 0.3 to about 6 wt.-%,

wt.-% with respect to the amount of the whole composition.

The adhesive composition described in the present text may also comprise filler. Adding a filler can be beneficial e.g. for adjusting the rheological properties like viscosity. The content of the filler also typically influences the physical properties of the composition after hardening, like hardness or flexural strength.

The chemical nature of the filler(s) is not particularly limited unless the intended purpose cannot be achieved.

The size of the filler particles should be such that a homogeneous mixture with the hardenable component forming the resin matrix can be obtained.

The particle size of the filler may be in a range from about 0.001 to about 10 μιη.

The filler(s) typically comprise non acid reactive fillers. A non-acid reactive filler is a filler which does not undergo an acid/base reaction with an acid.

Useful non acid reactive fillers include fumed silica, quartz, ground glasses, non- water-soluble fluorides such as CaF₂, silica gels such as silicic acid, in particular pyrogenic silicic acid and granulates thereof, cristobalite, calcium silicate, zirconium silicate, zeolites, including the molecular sieves, barium sulphate, yttrium fluoride. Suitable fumed silicas include for example, products sold under the tradename

Aerosil™ series OX-50, -130, -150, and -200, Aerosil R8200 available from Degussa AG, (Hanau, Germany), CAB-O-SIL™ M5 available from Cabot Corp (Tuscola, 111.), and HDK types, e.g. HDK-H 2000, HDK H15; HDK H18, HDK H20 and HDK H30 available from Wacker. The average surface area of the silica particles is preferably greater than about 15 m²/g more preferably greater than about 30 m²/g.

Filler(s) which can also be used include nano-sized fillers such as nano-sized silica.

Suitable nano-sized particles typically have a mean particle size in the range of about 5 to about 80 nm. Preferred nano-sized silicas are commercially available from Nalco Chemical Co.

(Naperville, 111.) under the product designation NALCO COLLOIDAL SILICAS (for example, preferred silica particles can be obtained from using NALCO products 1040, 1042, 1050, 1060, 2327 and 2329), Nissan Chemical America Company, Houston, Texas (for example, SNOWTEX-ZL, -OL, -O, -N, -C, -20L, -40, and -50); Admatechs Co., Ltd., Japan (for example, SX009-MIE, SX009-MIF, SC1050-MJM, and SC1050-MLV); Grace GmbH & Co. KG, Worms, Germany (for example, those available under the product designation LUDOX, e.g., P-W50, P-W30, P-X30, P-T40 and P-T40AS); Akzo Nobel Chemicals GmbH, Leverkusen, Germany (for example, those available under the product designation LEVASIL, e.g., 50/50%, 100/45%, 200/30%, 200A/30%, 200/40%, 200A/40%, 300/30% and 500/15%), and Bayer MaterialScience AG, Leverkusen, Germany (for example, those available under the product designation DISPERCOLL S, e.g., 5005, 4510, 4020 and 3030).

Surface-treating the nano-sized silica particles before loading into the dental material can provide a more stable dispersion in the resin. Preferably, the surface- treatment stabilizes the nano-sized particles so that the particles will be well dispersed in the hardenable resin and results in a substantially homogeneous composition. Furthermore, it is preferred that the silica be modified over at least a portion of its surface with a surface treatment agent so that the stabilized particle can copolymerize or otherwise react with the hardenable resin during curing.

Thus, the silica particles as well as other suitable non acid-reactive fillers can be treated with a resin-compatibilizing surface treatment agent.

Particularly preferred surface treatment or surface modifying agents include silane treatment agents capable of polymerizing with a resin. Preferred silane treatment agent include gamma-methacryloxylpropyltrimethoxysilane, available commercially under the trade designation A- 174, available commercially from Witco OSi Specialties (Danbury, Conn.) and gamma-glycidoxypropyltrimethoxy silane, a product available under the trade designation G6720, available from United Chemical Technologies (Bristol, Pa.).

Alternatively a combination of surface modifying agents can be useful, wherein at least one of the agents has a functional group co-polymerizable with a hardenable resin. For example, the polymerizing group can be ethylenically unsaturated or a cyclic function subject to ring opening polymerization. An ethylenically unsaturated polymerizing group can be, for example, an acrylate or methacrylate, or vinyl group. A cyclic functional group subject to ring opening polymerization generally contains a heteroatom such as oxygen, sulfur or nitrogen, and preferably is a 3-membered ring containing oxygen such as an epoxide. Other surface modifying agents which do not generally react with hardenable resins can be included to enhance dispersibility or rheological properties. Examples of silane of this type include, for example, alkyl or aryl polyethers, alkyl, hydroxy alkyl, hydroxy aryl, or amino alkyl functional silanes.

Besides an inorganic material the filler(s) can also be based on an organic material. Examples of suitable organic filler particles include filled or unfilled pulverized polycarbonates, poly(meth)acrylates, polyepoxides, and the like.

If desired, the measurement of the particle size of the filler particles can be done with a TEM (transmission electron microscopy) method, whereby a population is analyzed to obtain an average particle diameter. A preferred method for measuring the particle diameter can be described is as follows:

Samples approximately 80nm thick are placed on 200 mesh copper grids with carbon stabilized formvar substrates (SPI Supplies- a division of Structure Probe, Inc., West Chester, PA). A transmission electron micrograph (TEM) is taken, using JEOL 200CX (JEOL, Ltd. of Akishima, Japan and sold by JEOL USA, Inc.) at 200Kv. A population size of about 50-100 particles can be measured and an average diameter is determined.

The amount of filler to be used in the filler matrix usually depends on the purpose for which the composition should be used.

The filler is typically present in the following amounts:

- Lower limit: at least about 0 or at least about 1 or at least about 2 wt.-%

- Upper Limit: up to about 14 or up to about 10 or up to about 8 wt.-%

- Range: from about 0 to about 14 or from about 1 to about 10 or from about 2 to about 8 wt.-%,

wt.-% with respect to the amount of the whole composition.

The adhesive composition described in the present text may also comprise additives.

Besides the above mentioned components, the dental composition described in the present text may further contain one, two or more of the following additives: x-ray visible particles not being POM,

- pigments,

photobleachable colorants,

fluoride release agents,

- stabilizers,

- retarders,

and mixtures thereof.

Suitable x-ray visible particles which may be present in addition to the POM already contained in the dental composition described in the present text include particles of metal oxides like the oxides of yttrium, ytterbium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanide elements (i.e. elements having atomic numbers ranging from 57 to 71, inclusive), cerium and combinations thereof. Most preferably, the oxides of heavy metals having an atomic number greater than 30, but less than 72 are optionally included in the materials of the invention. Particularly preferred radiopacifying metal oxides include lanthanum oxide, zinc oxide, tin oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, cerium oxide, and combinations thereof.

Examples of pigments, which can be used include titanium dioxide or zinc sulphide (lithopones), red iron oxide 3395, Bayferrox 920 Z Yellow, Neazopon Blue 807 (copper phthalocyanine-based dye) or Helio Fast Yellow ER. These additives may be used for individual coloring of the dental compositions.

Examples of photobleachable colorants which can be present include Rose Bengal, Methylene Violet, Methylene Blue, Fluorescein, Eosin Yellow, Eosin Y, Ethyl Eosin, Eosin bluish, Eosin B, Erythrosin B, Erythrosin Yellowish Blend, Toluidine Blue, 4', 5'- Dibromofiuorescein and blends thereof. Further examples of photobleachable colorants can be found in US 6,444,725. The color of the compositions of the invention may be additionally imparted by a sensitizing compound.

Examples of fluoride release agents which can be present include naturally occurring or synthetic fluoride minerals. These fluoride sources can optionally be treated with surface treatment agents. Further additives, which can be added, include stabilizers, especially free radical scavengers such as substituted and/or unsubstituted hydroxyaromatics (e.g. butylated hydroxytoluene (BHT), hydroquinone, hydroquinone monomethyl ether (MEHQ), 3,5-di- tert-butyl-4-hydroxyanisole (2,6-di-tert-butyl-4-ethoxyphenol), 2,6-di-tert-butyl-4- (dimethylamino)methylphenol or 2,5-di-tert-butyl hydroquinone, 2-(2'-hydroxy-5'- methylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, 2- hydroxy-4-methoxybenzophenone (UV-9), 2-(2'-hydroxy-4',6'-di-tert-pentylphenyl)-2H- benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, 2-(2'-hydroxy-5'- methacryloxyethylphenyl)-2H-benzotriazole, phenothiazine, and HALS (hindered amine light stabilizers) .

Further additives, which can be added, include retarders, (such as 1,2- diphenylethylene), plasticizers (including polyethylene glycol derivatives, polypropylene glycols, low-molecular-weight polyesters, dibutyl, dioctyl, dinonyl and diphenyl phthalate, di(isononyl adipate), tricresyl phosphate, paraffin oils, glycerol triacetate, bisphenol A diacetate, ethoxylated bisphenol A diacetate, and silicone oils), fiavorants, anti-microbials, fragrance, agents that impart fluorescence and/or opalescence and fluoride releasing materials.

There is no need for the additive(s) to be present, however, if present, the additive(s) is(are) typically present in the following amounts:

- Lower limit: at least about 0 or at least about 0.01 or at least about 0.1 wt.-%

- Upper Limit: up to about 5 or up to about 4 or up to about 3 wt.-%

- Range: from about 0 to about 5 or from about 0.01 to about 4 or from about 0.1 to about 3 wt.-%,

wt.-% with respect to the amount of the whole composition.

According to a further embodiment, the adhesive dental composition described in the present text is described as follows:

- Polymerizable monomer (1): from about 5 to about 85 wt.-%, or from about 10 to about 80 wt.-%, or from about 15 to about 70 wt.-%;

- Polymerizable monomer (2): from about 1 to about 80 wt.-%, or from about 5 to about 70 wt.-%, or from about 10 to about 60 wt.-%; - Polymerizable monomer (3): from 0 to about 40 wt.-%, or from about 1 to about 30 wt.-%, or from about 5 to about 20 wt.-%;

- Solvent(s): from 0 to about 40 wt.-%, or from about 1 to about 30 wt.-%, or from about 5 to about 20 wt.-%;

- Initiator(s): from about 0.1 to about 10 wt.-%, or from about 0.2 to about 8 wt.-%, or from about 0.3 to about 6 wt.-%;

- Filler(s): from about 0 to about 14 wt.-%, or from about 0.1 to about 10 wt.-%, or from about 1 to about 8 wt.-%;

- Additive(s): from 0 to about 5 wt.-%, or from about 0.01 to about 4 wt.-%, or from about 0.1 to about 3 wt.-%;

wt.-% with respect to the weight of the whole composition.

The adhesive dental composition described in the present text can be produced as follows:

- providing the respective components,

- mixing the components.

Mixing can be achieved by using any means known to the practitioner. That is, the adhesive composition can be prepared in an one-pot synthesis simply by putting the respective components together and mixing them. If desired, the production process is performed under save light conditions to avoid an undesired polymerization of the composition.

The dental composition described in the present text is typically stored in a container until use. Depending on the formulation, various containers can be used. The composition can be provided in the form of a one-component system or as a two- component system. This typically depends on the initiator system chosen. As the composition is radiation curable, it is usually provided as a one-component system.

Low viscous compositions can be stored in a vial, bottle or blister. Suitable vials are described e.g. in EP 0 944 364 Bl and WO 2011/056814 Al . The content of these documents with respect to the description of the vial or bottle is herewith incorporated by reference.

Low viscous composition may also be stored in a container formed by two sheets, interconnected by hot sealing and cooperating to form a compartment for receiving the liquid and a pocket for receiving a brush i.e. a blister. These kind of devices are described e.g. in US 6,105,761.

The volume of the container is typically in the range from about 0.1 to about 100 ml or from about 0.5 to about 50 ml or from about 1 to about 30 ml.

The invention described in the present text is also directed to a kit of parts.

Such a kit typically comprises the adhesive dental composition described in the present text, dental composite or filling material, optionally an application device (e.g. brush or syringe) and optionally an instruction of use. The instruction of use typically contains hints to the practitioner how and under what conditions the adhesive composition should be applied to the surface of hard dental tissue.

The invention is also directed to the use of the composition described in the present text as dental material or for use in the dental field.

The dental composition is typically used in the mouth of a patient and is disposed adjacent to natural teeth. The phrase "disposed adjacent to" as used herein refers to the placing of a dental material in temporary or permanent bonding (e.g., adhesive) or touching (e.g., occlusal or proximal) contact with a natural tooth. The term "sealant" as used herein refers to a lightly filled dental composite or to an unfilled dental material that is cured after it is disposed adjacent to a tooth.

A typical application process for the composition described in the present text typically includes the following steps in the desired order:

• providing the composition, • placing the composition in contact with hard dental tissue, especially the surface thereof,

• curing the composition, e.g. by applying radiation (e.g. visible light) to the composition for a period of time sufficient to initiate the polymerisation process (e.g. about 5 to about 20 s).

If the composition is provided as a self-adhesive composition, no prior etching step or use of a bonding/primer is typically needed.

Suitable tools for applying radiation include dental curing lights. Suitable dental curing lights are described e.g. in US 2005/0236586. The content of this document is herewith incorporated by reference. Suitable dental curing lights are also commercially available e.g. under the trade names Elipar™ S10 (3M ESPE).

According to a particular embodiment, the dental composition described in the present text is characterized as follows:

- Polymerizable monomer(s) (1) being represented by the formula described in the present text in an amount from about 5 to about 85 wt.-%,

Polymerizable monomer(s) (2) being represented by the formula as described in the present text in an amount from about 1 to about 80 wt.-%,

Radiation curing initiator(s),

- Silica filler(s) in an amount from about 0 to about 10 wt.-%.

All components used in the dental composition of the invention should be sufficiently biocompatible, that is, the composition should not produce a toxic, injurious, or immunological response in living tissue. The complete disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each were individually incorporated. Various modifications and alterations to this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. The above specification, examples and data provide a description of the manufacture and use of the compositions and methods of the invention. The invention is not limited to the embodiments disclosed herein. One skilled in the art will appreciate that many alternative embodiments of the invention can be made without departing from the spirit and scope of thereof.

The following examples are given to illustrate, but not limit, the scope of this invention. Unless otherwise indicated, all parts and percentages are by weight.

Examples

Unless otherwise indicated, all parts and percentages are on a weight basis, all water is deionized water, and all molecular weights are weight average molecular weight. Moreover, unless otherwise indicated all Experiments were conducted at ambient conditions (23°C; 1013 mbar). Moreover, nearly all process steps are conducted under an atmosphere of dry air:

Storage Stability

If desired, storage stability can be determined as follows: The composition is stored at elevated temperatures and / or different ambient humidity levels in the intended packaging. At certain time intervals, characteristic features such as adhesion, visual appearance, or mechanical strength is determined. For accelerated aging e.g. storage at 50 °C can be used.

Adhesion 1 (Adl)

If desired, the initial adhesion to dentin or enamel can be determined according to

ISO/FDIS 29022:2012(E) of the freshly prepared dental formulation.

Adhesion 2 (Ad2)

If desired, the Storage Stability of the adhesion to dentin or enamel can be determined according to ISO/FDIS 29022:2012(E) of the accelerated aged dental formulation that was stored for four months at a temperature of 50 °C.

Abbreviations

The name and/or structure of the components used are given in Table 1.

Table 1

OT-A/MA/AM

MGS-A/MA/AM

MGiS-A/MA/AM

MGT-A/MA/AM

02oHB-

A/MA/AM

OE2oHB-

A/MA/AM

E4pHB-

A/MA/AM

Resorcinol 1,3-dihydroxybenzene, CAS 108-46-3, EC 203-585-2 R

Catechol 1,2-dihydroxybenzene, CAS 120-80-9, EC 204-427-5 C

Tert-butylcatechol 4-tert-butylcatechol, 4-tert-butyl- 1,2-dihydroxybenzene, CAS BC

98-29-3, EC 202-653-9

Tyrosol 4-(2-hydroxyethyl)phenol, 2-(4-hydroxyphenyl)ethanol, CAS T

501-94-0, EC 207-930-8

Salicyl alcohol 2-hydroxybenzyl alcohol, 2-hydroxymethylphenol, Saligenin, S

CAS 90-01-7, EC 201-960-5 iso-Salicyl alcohol 3-hydroxybenzyl alcohol, 3-hydroxymethylphenol, CAS 620- iS

24-6, EC 210-633-6

Resorcinol 3-hydroxyphenyl acetate, CAS 102-29-4 , EC 203-022-0 RAc monoacetate

Resorcinol 1,3-diacetoxybenzene, CAS 108-58-7, EC 203-596-2 RAc2 diacetate ortho- Salicylic acid, 2-hydroxybenzoic acid, CAS 69-72-7, EC 200- oHB

Hydroxybenzoic 712-3

Acid meta- Iso-Salicylic acid, 3-hydroxybenzoic acid, CAS 99-06-9, EC mHB

Hydroxybenzoic 202-726-5

Acid para- 4-hydroxybenzoic acid, CAS 99-96-7, EC 202-804-9 pHB

Hydroxybenzoic

Acid

2-chloroethanol Ethylene chlorohydrin , CAS 107-07-3, EC 203-459-7 3-chloro-l- l-chloro-3-hydroxypropane, CAS 627-30-5, EC 210-992-9

propanol

2-(2- 3-oxa-5-chloro-l-pentanol , CAS 628-89-7, EC 211-059-9

chloroethoxy)ethan

ol

5-chloro-l- Pentamethylene chlorohydrin , CAS 5259-98-3, EC 226-067- pentanol 8

6-chloro- 1 -hexanol Hexamethylene chlorohydrin , CAS 2009-83-8, EC 217-925-2

Ethylene carbonate l,3-Dioxolan-2-one, CAS 96-49-1, EC 202-510-0

Glycidyl phenyl 2-(phenoxymethyl)oxirane , 2,3-epoxypropyl phenyl ether, GP ether phenyl glycidyl ether, CAS 122-60-1, EC 204-557-2

Glycidyl 2,3-Epoxypropyl methacrylate, Methacrylic acid 2,3- GMA methacrylate epoxypropyl ester , CAS 106-91-2, EC 203-441-9

Acrylic acid Propenoic acid , CAS 79-10-7, EC 201-177-9 AA

Methacrylic acid 2-Methacrylic acid, 2-Methylpropenoic acid , CAS 79-41-4, MA

EC 201-204-4

Methanesulfonic CAS 75-75-2, EC 200-898-6 MSA acid

Tetrahydrofuran CAS 109-99-9, EC 203-726-8 THF iso-Propanol 2-propanol , CAS 67-63-0, EC 200-661-7 IPA tert-Butanol 2-methyl-2-propanol , CAS 75-65-0, EC 200-889-7 HOtBu

Potassium tert- Potassium tert-butylate , CAS 865-47-4, EC 212-740-3 KOtBu butoxide

Sodium hydroxide CAS 1310-73-2, EC 215-185-5 NaOH

Potassium CAS 1310-58-3, EC 215-181-3 KOH hydroxide Methyl tert-butyl tert-Butyl methyl ether , CAS 1634-04-4, EC 216-653-1 MTBE ether

Ethyl acetate Acetic acid ethyl ester , CAS 141-78-6, EC 205-500-4 EA

Methyl ethyl Ethyl methyl ketone, 2-butanone , CAS 78-93-3, EC 201-159- MEK ketone 0

2,6-di-tert-Butyl-4- 2,6-Di-tert-butyl-p-cresol, Butylated hydroxytoluene, BHT methylphenol Butylhydroxytoluene, DBPC, CAS 128-37-0, EC 204-881-4 hydroquinone 1 ,4-dihydroxybenzene , 1 ,4-benzenediol, CAS 123-31-9, EC HQ

204-617-8

Hydroquinone 4-methoxyphenol, 4-Hydroxyanisole, 4-MP, HQMME, HQME monomethyl ether MEHQ, MQ-F , CAS 150-76-5, EC 205-769-8

Methylene blue 3,7-bis(Dimethylamino)phenazathionium chloride, Basic Blue

9, Tetramethylthionine chloride , CAS 7220-79-3, EC 200- 515-2

Sodium carbonate CAS 497-19-8, EC 207-838-8 Na2CO

3

Potassium CAS 584-08-7, EC 209-529-3 K2C03 carbonate

CPQ Camphorquinone (CAS no. 10373-78-1) Inil

EDMAB Ethyl 4-dimethylaminobenzoate (CAS no. 10287-53-3) Ini2

DMAEMA 2-Dimethylaminoethyl methacrylate (CAS no. 2867-47-2) Ini3

HEMA 2-Hydroxyethyl methacrylate (CAS no. 868-77-9) Col

MDP reaction products of methacrylic acid with 1,10-decanediol Co2 and phosphorous oxide (P2O5) (CAS no. 1207736-18-2)

VBCP Vitrebond™ Copolymer; prepared according to Example 11 Co3 of US 5,130,347 (CAS no. 25948-33-8)

Filler Aerosil™ 200 fumed silica (CAS no. 112945-52-5) Filler MPS 3-Methacryloxypropyl trimethoxysilane (CAS no. 2530-85-0) Silane

Water Water (CAS no. 7732-18-5) Solvl

Ethanol Ethanol (CAS no. 64-17-5) Solv2

Triphenylphosphan Triphenylphosphine, CAS no. 603-35-0, EC 210-036-0 PPhs e

Triethylamine CAS no. 121-44-8, EC 204-469-4 TEA

General Procedure A: Synthesis of Diol Precursors (e.g. OR or E2T) via Etherification of Dihydroxybenzenes (e.g. Resorcinol) or Hydroxyalkylphenols (e.g. Tyrosol) Hydroxybenzoic Acids (e.g. mHB) or via Nucleophilic Esterification of Hydroxybenzoic Acids (e.g. mHB) with Halogenated Alcohols (e.g. 3-Chloro-l-propanol)

To a solution of the corresponding Dihydroxybenzene or Hydroxyalkylphenol and the corresponding Halogenated Alcohol/s in water an aqueous solution of alkaline hydroxide (e.g. NaOH) or alkaline carbonate (e.g. Na2C03) or ammonia is added at reflux. Optionally the synthesis can be done under a protective gas atmosphere (e.g. nitrogen).

Alternatively IPA or tBuOH can be used as solvent and solid alkaline hydroxide (e.g. KOH) or alkaline carbonate (e.g. Na2C03) as base.

Also a subsequent reaction pattern is possible for Dihydroxybenzenes or Dihydroxybenzene Monoesters (e.g. RAc) where in the first reaction step one equivalent of base and one half of the Halogenated Alcohol/s is reacted with the Dihydroxybenzene or Dihydroxybenzene Monoester and afterwards in the second reaction step another equivalent of base and the remaining half of the Halogenated Alcohol/s is reacted (if a Dihydroxybenzene Monoester is used then after the first reaction step an ester hydrolysis, e.g. a basic ester hydrolysis, has to be done before the second reaction step can occur). After stirring over night at reflux the reaction mixture is cooled to room temperature, and the reaction mixture is extracted (e.g. MTBE or EA or MEK) if water is used as solvent. Optionally the reaction mixture can be extracted as it is or the organic phase can be separated and only the aqueous phase can be extracted, afterwards the organic phase is combined with the extracts. Optionally the combined organic phases can be extracted with aqueous alkaline (e.g. NaOH) solutions and/or aqueous acid (e.g. H2S04) solutions and/or water.

If IPA or tBuOH is used as solvent the reaction mixture is first filtered to remove the precipitate, then the solvent is stripped off in vacuo, and then the residue is extracted against water as described above.

If a Hydroxybenzoic Acid is used as building block first the reaction mixture is acidified with aqueous acid (e.g H2S04) and then extracted against water as described above to isolate the etherification product Hydroxyalkoxybenzoic Acid and/or the nucleophilic esterification product Hydroxybenzoic Acid Hydroxyalkyl Ester.

Optionally the combined organic phases are filtered through silica or alumina and/or are stirred with charcoal to achieve improved decolorization. After drying over anhydrous Na2S04 and filtration the solvent is stripped off in vacuo.

Alternatively an alkylation according to the so-called Carbonate Method according to Houben-Weyl, Methoden der Organischen Chemie, Band VI/3 Teil 3, Sauerstoffverbindungen 1, 4. Auflage, 1965, Georg Thieme Verlag, Stuttgart, p. 55, or a deacylating alkylation of mono or diacylated Dihydroxybenzenes (e.g. RAc or RAc2) according to Houben-Weyl, Methoden der Organischen Chemie, Band VI/3 Teil 3, Sauerstoffverbindungen 1, 4. Auflage, 1965, Georg Thieme Verlag, Stuttgart, p. 59, is possible.

General Procedure B: Synthesis of Diol Precursors (e.g. PER) via Etherification of Already Alkoxylated Dihydroxybenzenes (e.g. ethoxylated resorcinol) with Halogenated Alcohols (e.g. 3-Chloro-l-propanol)

Under a protective gas atmosphere (e.g. nitrogen) to a mixture of the corresponding Already Alkoxylated Dihydroxybenzene and the corresponding Halogenated Alcohol/s a solution of KOtBu in e.g. THF or tBuOH is added slowly at elevated temperature (e.g. 80°C). After stirring over night at elevated temperature the reaction mixture is cooled to room temperature, the precipitate is separated by filtration, and the solvent is stripped off from the filtrate in vacuo. Optionally further purification of this residue via an aqueous workup as described in General Procedure A can be achieved. General Procedure C: Synthesis of Ethoxylated Diol Precursors (e.g. ET) via Etherification of Hydroxyalkylphenols (e.g. Tyrosol) with Ethylene Carbonate

To a solution of the corresponding Hydroxyalkylphenol and Ethylene Carbonate in IPA or tBuOH solide alkaline hydroxide (e.g. KOH) or alkaline carbonate (e.g. K2C03) or alkaline tert-butoxide (e.g. KOtBu) is added and the reaction mixture is stirred at reflux over night. Optionally the synthesis can be done under a protective gas atmosphere (e.g. nitrogen).

The reaction mixture is cooled to room temperature, the solvent is stripped off in vacuo, and then the residue is extracted against water and further worked up as described in General Procedure A. Optionally the isolated product can be further purified by crystallization using water as solvent.

General Procedure D: Synthesis of Diol Precursors (e.g. PGT) via Addition of Dihydroxybenzenes (e.g. 4-tert-Butylcatechol) or Hydroxyalkylphenols (e.g. Tyrosol) or Hydroxybenzoic Acids (e.g. mHB) or Already Etherified and/or Nucleophilic Esterified Hydroxybenzoic Acids (e.g. OmHB) onto Epoxies (e.g. GP or GMA) under Ring-Opening

Solvent Base Route: To an aqueous solution of the corresponding Hydroxyalkylphenol (e.g. Tyrosol) and alkaline hydroxide (e.g. NaOH) or alkaline carbonate (e.g. Na2C03) or ammonia the epoxy (e.g. GP) is added at reflux. Optionally the synthesis can be done under a protective gas atmosphere (e.g. nitrogen). Optionally the synthesis can be done using IPA or HOtBu as solvent and solid alkaline hydroxide (e.g. KOH) or alkaline carbonate (e.g. K2C03) or alkaline tert-butoxide (e.g. KOtBu). After stirring over night at reflux the reaction mixture is cooled to room temperature, and the reaction mixture is extracted and further worked up as described in General Procedure A.

Solvent Free Route: To the mixture of the corresponding Dihydroxybenzenes (e.g. 4-tert- Butylcatechol) and the epoxy (e.g. GMA) a catalyst (e.g. PPh₃ or TEA) is added under stirring and the reaction mixture is warmed to an elevated temperature. Optionally the synthesis can be done under a protective gas atmosphere (e.g. nitrogen). After stirring over night at elevated temperature the reaction mixture is cooled to room temperature, and the reaction mixture is extracted and further worked up as described in General Procedure A. Optionally the isolated product can be further purified by crystallization using water as solvent or by fractionated subsequent organic-organic extraction using organic solvents of different polarities.

General Procedure E: Acid Catalyzed (e.g. MSA) Esterification of Diol Precursors (e.g. OR) with Unsaturated Acids (e.g. MA)

To the corresponding Diol Precursor in e.g. cyclohexane or a hexane/toluene mixture or a cyclohexane/toluene mixture BHT , HQME, optionally methylene blue and/or HQ, the catalyst (e.g. MSA) and the unsaturated acid (e.g. MA) are added. At reflux water is removed using a Dean Starck apparatus. After completion of the reaction the crude reaction mixture is extracted at least twice with 4N NaOH solution or 2N NaOH solution, then at least once washed with water, and then dried over anhydrous Na2S04. After filtration, the filtrate is optionally filtered through basic alumina. 100-300 ppm of BHT and 100-300 ppm of HQME are added to the filtrate. Then the solvent is stripped off in vacuo while air is bubbling through the crude sample.

R-MA (Comparative Example 1):

Synthesis according to literature US 3,853,962, Example 1.

BisGMA (Comparative Example 2):

Commercially available monomer. ER-MA (Comparative Example 3):

According to General Procedure E 118.6 g of ER, 13.0 g of MSA, and 150.3 g of MA were reacted to give 148.2 g of ER-MA as a yellowish oil that crystallizes at room temperature readily to a colorless solid (m.p. > 60°C).

EH-MA (Comparative Example 4): According to General Procedure E 118.6 g of EH, 13.0 g of MSA, and 150.3 g of MA were reacted to give 118.3 g of EH-MA as a colorless solid (m.p. > 80°C) immediately after synthesis.

EER-MA (Inventive Example 1): According to the subsequent reaction pattern of General Procedure A first 50.0 g of resorcinol, 27.5 g of NaOH, and 55.4 g of 2-chloro-l-ethanol were reacted over night at a reaction temperature of 40 °C in 155 mL of water, then 75.0 g of 2-(2-chloroethoxy)- ethanol and 27.5 g of NaOH dissolved in 44.4 mL of water were added under reflux and the reaction mixture was kept at reflux over night to give 78.2 g of EER. According to General Procedure E 74.0 g of EER, 5.20 g of MSA, and 78.9 g of MA were reacted to give 105.5 g of EER-MA.

OER-MA (Inventive Example 2):

According to General Procedure B 60.0 g of ethoxylated resorcinol (ER), 31.5 g of 3-chloro-l-propanol, and 165.4 g of a 1.7M KOtBu solution in THF were reacted to give 63.5 g of OER. According to General Procedure E 85.0 g of OER, 5.80 g of MSA, and 85.7 g of MA were reacted to give 117.6 g of OER-MA.

OOR-MA (Inventive Example 3):

According to General Procedure B 20.0 g of OR, 8.53 g of 3-chloro-l-propanol, and 88.4 mL of a 1M KOtBu solution in HOtBu were reacted to give 20.3 g of OOR. According to General Procedure E 17.0 g of OOR, 1.10 g of MSA, and 15.4 g of MA were reacted to give 23.2 g of OOR-MA.

OE2R-MA (Inventive Example 4):

According to General Procedure A 51.0 g of resorcinol, 47.7 g of NaOH, 69.2 g of 2-(2-chloroethoxy)-ethanol, and 51.5 g of 3-chloro-l-propanol were reacted in 200 mL of water to give 93.5 g of OE2R. According to General Procedure E 55.0 g of OE2R, 3.80 g of MSA, and 55.4 g of MA were reacted to give 71.4 g of OE2R-MA.

HOR-MA (Inventive Example 5):

According to General Procedure A 51.0 g of resorcinol, 47.7 g of NaOH, 75.9 g of 6-chlorohexanol and 51.5 g of 3-chloro-l-propanol were reacted in 200 mL of water to give 115.2 g of HOR. According to General Procedure E 70.0 g of HOR, 4.67 g of MSA, and 67.4 g of MA were reacted to give 101.7 g of HOR-MA. HOR-A (Inventive Example 6):

According to General Procedure E 43.7 g of HOR, 2.68 g of MSA, and 35.2 g of acrylic acid (AA) were reacted to give 54.8 g of HOR-A.

POR-MA (Inventive Example 7): According to General Procedure A 51.0 g of resorcinol, 47.7 g of NaOH, 68.2 g of

5-chloropentanol, and 51.5 g of 3-chloro-l-propanol were reacted in 200 mL of water to give 85.2 g of POR. According to General Procedure E 81.9 g of POR, 5.60 g of MSA, and 83.2 g of MA were reacted to give 119.8 g of POR-MA.

OE2C-MA (Inventive Example 8): According to General Procedure A 50.0 g of catechol, 49.0 g of NaOH, 75.0 g of

2-(2-chloroethoxy)-ethanol, and 51.5 g of 3-chloro-l-propanol were reacted in 200 mL of water to give 67.7 g of OE2C. According to General Procedure E 65.0 g of OE2C, 4.40 g of MSA, and 65.5 g of MA were reacted to give 88.3 g of OE2C-MA.

E4RE-MA (Inventive Example 9): According to General Procedure A 48.8 g of l,3-dihydroxy-4-ethylbenzene, 64.0 of KOH, and 113.2 g of 2-(2-chloroethoxy)-ethanol were reacted in 280 mL of water to give 58.7 g of E4RE. According to General Procedure E 57.6 g of E4RE, 3.57 g of MSA, and 47.3 g of MA were reacted to give 71.4 g of E4RE-MA.

E4RH-MA (Inventive Example 10): According to General Procedure A 68.6 g of l,3-dihydroxy-4-hexylbenzene, 39.2 of NaOH, and 113.2 g of 2-(2-chloroethoxy)-ethanol were reacted in 275 mL of water to give 110.0 g of E4RH. According to General Procedure E 107.0 g of E4RH, 6.20 g of MSA, and 74.6 g of MA were reacted to give 108.2 g of E4RH-MA.

ORE-MA (Inventive Example 11): According to General Procedure A 49.6 g of 4-ethylresorcinol, 37.7 g of NaOH, and 81.4 g of 3-chloro-l-propanol were reacted in 200 mL of water to give 76.2 g of ORE. According to General Procedure E 72.4 g of ORE, 5.00 g of MSA, and 73.5 g of MA were reacted to give 107.4 g of ORE-MA. ORH-MA (Inventive Example 12):

According to General Procedure A 32.9 g of 4-hexylresorcinol, 17.8 g of NaOH, and 37.7 g of 3-chloro-l-propanol were reacted in 130 mL of water to give 39.8 g of ORH. According to General Procedure E 39.8 g of ORH, 1.13 g of MSA, and 33.1 g of MA were reacted to give 54.8 g of ORH-MA.

EBC-MA (Inventive Example 13):

According to General Procedure C 30.0 g of 4-tert-butylcatechol, 3.54 g of KOH, and 47.7 g of ethylene carbonate were reacted in 40 g of IPA to give 46.5 g of EBC. According to General Procedure E 46.0 g of EBC, 2.89 g of MSA, and 38.9 g of MA were reacted to give 65.8 g of EBC-MA.

EEBC-MA (Inventive Example 14):

According to the subsequent reaction pattern of General Procedure A first 37.4 g of 4-tert-butylcatechol, 13.5 g of NaOH, and 27.1 g of 2-chloro-l-ethanol were reacted over night at a reaction temperature of 40 °C in 128 mL of water, then 36.4 g of 2-(2- chloroethoxy)-ethanol and 13.5 g of NaOH dissolved in 22 mL of water were added under reflux and the reaction mixture was kept at reflux over night to give 59.4 g of EEBC. According to General Procedure E 59.4 g of EEBC, 3.77 g of MSA, and 51.4 g of MA were reacted to give 71.8 g of EEBC-MA.

E4BC-MA (Inventive Example 15): According to General Procedure A 76.2 g of 4-tert-butylcatechol, 47.7 of NaOH, and 138.5 g of 2-(2-chloroethoxy)-ethanol were reacted in 300 mL of water to give 124.9 g of E4BC. According to General Procedure E 58.7 g of E4BC, 3.50 g of MSA, and 44.3 g of MA were reacted to give 45.7 g of E4BC-MA.

OBC-MA (Inventive Example 16): According to General Procedure A 77.0 g of 4-tertbutylcatechol, 48.2 of NaOH, and 105.1 g of 3-chloro-l-propanol were reacted in 300 mL of water to give 119.1 g of OBC. According to General Procedure E 60.0 g of OBC, 3.91 g of MSA, and 54.9 g of MA were reacted to give 81.0 g of OBC-MA. OE2BC-MA (Inventive Example 17):

According to General Procedure A 69.6 g of 4-tertbutylcatecfiol, 45.3 g of NaOH, 67.8 g of 2-(2-chloroethoxy)-ethanol, and 47.1 g of 3-chloro-l-propanol were reacted in 275 mL of water to give 113.2 g of OE2BC. According to General Procedure E 56.7 g of OE2BC, 3.50 g of MSA, and 46.9 g of MA were reacted to give 67.3 g of OE2BC-MA.

BC-GMA (Inventive Example 18):

According to General Procedure D (Solvent Free Route) 50.0 g of 4-tert- butylcatechol, 0.68 g of TEA, and 85.5 g of GMA were reacted at a temperature of 80 °C to give 114.6 g of BC-GMA. PGT -AM (Inventive Example 19):

According to General Procedure D (Solvent Based Route) 100.0 g of tyrosol, 5.73 g of NaOH, and 108.0 g of GP were reacted in 200 mL of water to give 203.4 g of crude PGT. After re-crystallization from water 188.9 g of purified PGT were collected. According to General Procedure E 218.5 g of purified PGT and 12.5 g of MSA were first reacted with 68.5 g of MA and then reacted with 82.0 g of AA to give 295.2 g of PGT- AM.

ET-MA (Inventive Example 20):

According to General Procedure C 100.0 g of tyrosol, 7.02 g of KOH, and 82.0 g of ethylene carbonate were reacted in 100 g of IPA to give 112.5 g of crude ET. After re- crystallization from water 74.5 g of purified ET were collected. According to General Procedure E 20.0 g of purified ET, 1.48 g of MSA, and 23.6 g of MA were reacted to give 33.2 g of ET-MA.

E2T-MA (Inventive Example 21):

According to General Procedure A 50.0 g of tyrosol, 44.9 og NaOH, and 136.6 g of 2-(2-chloroethoxy)-ethanol were reacted in 200 mL of water to give 88.1 g of E2T. According to General Procedure E 60.0 g of E2T, 2.80 g of MSA, and 22.8 g of MA were reacted to give 85.2 g of E2T-MA. OT-MA (Inventive Example 22):

According to General Procedure A 40.0 g of tyrosol, 19.7 og KOH, and 34.9 g of 3-chloro-l-propanol were reacted in 40 g of IPA to give 49.7 g of OT. According to General Procedure E 49.70 g of OT, 3.54 g of MSA, and 54.4 g of MA were reacted to give 79.7 g of OT-MA.

MGT-MA (Inventive Example 23):

According to General Procedure D (Solvent Based Route) 51.0 g of tyrosol, 10.9 mL of a 1M KOtBu solution in HOtBu, and 46.8 g of GMA were reacted to give 37.2 g of crude MGT. After fractionated subsequent organic-organic extraction using toluene/hexane mixtures as well as pure cyclohexane and pure hexane to remove unwanted very unpolar as well as unwanted very polar by-products 9.50 g of purified MGT-MA were collected.

Preparation of Adhesive Compositions Some of the compounds synthesized were used for producing a (dental) composition.

The compositions produced and tested with respect to their mechanical properties are given in Table 2 below. In Table 2 the values of the components represent wt.-% of the individual components in the corresponding dental formulation. General Procedure I:

A mixture of 19.7 g of CE or IE, 13.3 g of ethanol, 11.3 g of distilled water, 23.2 g of HEMA, 15.9 g of MDP, 0.71 g of DMAEMA, 0.10 g of BHT, 1.62 g of CPQ, 1.02 g of EDMAB, 2.00 g of VBCP, 8.10 g of fumed silica, and 3.00 g of MPTS was stirred for 6 hours at room temperature until a homogeneous solution was obtained. ("CE" stands for the respective component outlined as comparative example above; "IE" stands for the respective component outlined as inventive example above.)

Dental Compositions A and B contain either of Components CE1 and CE2 but not compound (A) according to the invention. In Tables 2 and 3 below, Compound (A) is represented by components IE1, IE4, IE8, IE9, IE13, IE14, IE18, IE19, IE20, IE21, IE22, and IE23. Thus, Dental Compositions A and B can be considered as Comparative Examples/Compositions, whereas Dental Compositions C to N can be considered as Inventive Examples/Compositions. Table 2

*) after four months of storage at 50 °C the dental formulation did not work anymore; thus no adhesion could be measured.

Table 3

As can be seen, compositions containing Compound (A) according to the invention are superior with respect adhesion even after storing the composition under severe conditions (i.e. "accelerated aging conditions") compared to compositions not containing Compound (A) according to the invention.

Claims

1. An adhesive dental composition comprising

Polymerizable monomer (1),

Polymerizable monomer (2) comprising an acidic moiety,

Initiator component(s),

Filler component(s) in an amount of less than about 15 wt.-%, wt.-% with respect to the whole weight of the composition,

the polymerizable monomer (1) being characterized by formula (I)

with:

B-0-A-[-0-B'-]a representing an unsymmetrical monomer backbone as linkage between the reactive (meth)acrylate moieties,

a = 0 or 1 ,

A being selected from:

A being always attached as aryl-alkyl ether onto B and / or B', B being selected from: *-(CH₂)b-* , *-(CH₂-CH₂-0-CH₂-CH₂ -* , *-(CH₂-CH₂-0-CH₂-CH₂-CH₂)-* , *-

(CH₂-CH₂-CH₂-0-CH₂-CH₂-CH₂₎_* ,

,

B' being selected from *-(CH2)_b -* , *-(CH₂-CH₂-0-CH₂-CH₂)-* ,

R = H, methyl,

X being selected from H, methyl, ethyl, hexyl, tert-butyl,

"*" representing those site(s) of a moiety of the monomer, where that moiety is bonded to another moiety of the monomer.

2. The adhesive dental composition according to any of claim 1, the polymerizable monomer (1) being characterized by either formula (la) or formula (lb)

with:

B-O-A-O-B' being an unsymmetrical monomer backbone as linkage between the reactive (meth)acrylate moieties,

A bein selected from

A being always attached as aryl-alkyl ether onto B and B',

B being selected from: *-(CH₂)b-* , *-(CH₂-CH₂-0-CH₂-CH₂)-* , *-(CH₂-CH₂-0-CH₂-CH₂-CH₂)-* , *-

OH

(CH₂-CH₂-CH₂-0-CH₂-CH₂-CH₂₎_* ,

B' being selected from: *-(CH2)_b -* , *-(CH₂-CH₂-0-CH₂-CH₂)-* ,

R = H, methyl,

X = H, methyl, ethyl, hexyl, tert-butyl; or

with:

B-O-A being an unsymmetrical monomer backbone as linkage between the reactive (meth)acrylate moieties,

A ing selected from:

B being selected from: *-(CH₂)b-* , *-(CH₂-CH₂-0-CH₂-CH₂)-* , ^"

,

R = H, methyl;

3. The adhesive dental composition according to any of claim 1 to 2 being characterized by at least one of the following features:

the polymerizable monomer (1) having a molecular weight of about 300 to about 600;

the polymerizable monomer (1) not solidifying at 23°C;

the adhesive composition having a pH value of less than about 4, if brought in contact with water;

being liquid at 23°C and 1013 mbar.

4. The adhesive dental composition according to any of claim 1 to 3, the polymerizable monomer 1) being selected from one of the following monomers

and mixtures thereof:

5. The adhesive dental composition according to any of claim 1 to 3, the polymerizable monomer (1) being selected from one of the following monomers and mixtures thereof:

R being always independently selected from H and CH3.

The adhesive dental composition according to any of claim 1 to 5, the polymerizable monomer (2) with an acidic moiety being selected from a component which is characterized by the following formula and mixtures thereof:

with A being an ethylenically unsaturated group, such as a (meth)acryl moiety, B being a spacer group, such as (i) linear or branched CI to C12 alkyl, optionally substituted with other functional groups (e.g. halogenides (including CI, Br, I), OH or mixtures thereof) (ii) C6 to C12 aryl, optionally substituted with other functional groups (e.g. halogenides, OH or mixtures thereof), (iii) organic group having 4 to 20 carbon atoms bonded to one another by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl and/or sulfonyl linkages, and

C being an acidic group, m, n being independently selected from 1, 2, 3, 4, 5 or 6, wherein the acidic group C comprises one or more carboxylic acid residues, phosphoric acid residues, phosphonic acid residues, sulphonic acid residues, or sulfuric acid residues.

7. The adhesive dental composition according to any of claim 1 to 6, the initiator being selected from radiation, heat curing initiators and combinations thereof.

8. The adhesive dental composition according to any of claim 1 to 7 comprising in addition at least one or more of the following component(s):

Polymerizable monomer (3) without an acidic moiety being different from polymerizable monomer (1),

- Additive(s).

9. The adhesive dental composition according to any of claim 1 to 8 comprising the respective components in the following amounts:

Polymerizable monomer(s) (1): from about 5 to about 85 wt.-%,

Polymerizable monomer(s) (2): from about 1 to about 80 wt.-%,

Polymerizable monomer(s) (3): from 0 to about 70 wt.-%,

Initiator(s): from about 0.1 to about 10 wt.-%,

Filler(s): from about 0 to about 14 wt.-%,

- Additive(s): from 0 to about 5 wt.-%.

10. The adhesive dental composition according to any of claim 1 to 9 not comprising acid reactive filler(s).

11. The adhesive dental composition according to any of claim 1 to 10, the adhesive composition being characterized by at least one or all of the following features before curing:

- Viscosity: from about 0.05 to about 5 Pa*s at 23°C;

pH value if brought in contact with water: about 0 to about 3,

- radiation curing,

storage stable,

being provided as a one-component mixture.

12. The adhesive dental composition according to any of claim 1 to 11, the adhesive composition being characterized by at least one or all of the following features after curing:

Adhesion of the composition to dentin: determined according to ISO 29022:2013: at least about 25 MPa;

- Adhesion of the composition to enamel: determined according to wire ISO

29022:2013: at least about 18 MPa;

Adhesion of the composition after storage for 4 months at 50°C to dentin: determined according to wire ISO 29022:2013: at least about 12 MPa;

Adhesion of the composition after storage for 4 months at 50°C to enamel: at least about 5 MPa.

13. The adhesive dental composition according to any of claim 1 to 12 being characterized as follows:

Polymerizable monomer(s) (1) being represented by the formula as described in any of claims 2 to 5 in an amount from about 5 to about 85 wt.-%,

Polymerizable monomer(s) (2) being represented by the formula as described in claim 6 in an amount from about 1 to about 80 wt.-%,

Radiation curing initiator(s), Silica filler(s) from about 0 to about 14 wt.-%.

14. Use of the adhesive dental composition as described in any of the proceeding claims as dental adhesive, sealant, cement or for bonding or cementing a material to the surface of hard dental tissue.