Hardenable composition for dental impressions

Abstract

The present invention relates to a hardenable composition for dental impressions comprising a hardenable base composition and a surfactant system comprising a first surfactant, which is at least one compound having formula (I), and a second surfactant, wherein the first surfactant acts synergistically with the second surfactant to enable the composition to have a surprisingly lower contact angle; these results are achieved with a relatively low concentration of biodegradable surfactant. [Formula 1] TIFF2023502479000042.tif60162

Description

[Technical Field]

[0001] The present invention relates to a hardenable composition for dental impressions and its use. The present invention also relates to a method for taking an impression. [Background technology]

[0002] Room temperature vulcanizing silicone rubbers (RTV) are known as dental impression materials, especially for their mechanical and elastic properties. Furthermore, addition silicones have good dimensional stability several days after the impression is taken.

[0003] Addition-type silicone impression materials are usually made from vinyl-terminated polysiloxanes and crosslinkers with Si—H groups in their chains, which typically react in the presence of a platinum catalyst (hydrosilylation reaction—see, for example, U.S. Pat. No. 7,592,377 B2, Dental Materials and Their Selection, William J. O'Brien, Quintessence Publishing Co.—ISBN-13:978-0867154375).

[0004] Another class of impression materials are condensation type silicone impression materials, which are usually made with hydroxy-terminated polysiloxanes and alkoxysilane crosslinkers, which usually react in the presence of a tin catalyst (see, for example, Dental Materials and Their Selection, William J. O'Brien, Quintessence Publishing Co. - ISBN-13:978-0867154375, U.S. Pat. No. 4,389,496 A, U.S. Pat. No. 5,925,723 A, U.S. Pat. No. 6,218,461 B1).

[0005] Fillers and additives are typically added to both addition and condensation type silicones to improve their mechanical performance or to obtain specific organoleptic properties.

[0006] The use of surfactants in particular is known to improve the compatibility of impression materials with oral tissues. Fluid materials, termed extralite, light, regular or monophase, therefore easily penetrate the gingival sulcus and reproduce the peripheral sulcus details well.

[0007] The performance of surfactants in dental impression materials is evaluated by contact angle measurements, particularly the sessile drop method, using the following equation: [ka] The use of a modified trisiloxane polyalkylene oxide superspreading surfactant having the formula: was reported in US Pat. No. 4,657,959.

[0008] Modified trisiloxane polyalkylene oxides are a powerful class of surfactants because they simultaneously possess a fairly high effectiveness in reducing surface tension (approximately 20 mN / m) and a very high spreading area, especially relative to other surfactants that have a more pronounced effect in reducing surface tension (Kovalchuk et al., Fluoro vs. Hydrocarbon Surfactants: Why Do They Differ in Wetting Performance? Advances in Colloid and Interface Science, Vol. 210 (2014), pp. 65-71).

[0009] Its effectiveness as a super-diffusing agent is reduced when it is encased in a matrix, which is caused by its lower ability to migrate to the impression material surface.

[0010] Modified trisiloxane polyalkylene oxides cannot reach their critical wetting concentration (CWC) when dispersed in complex mixtures of components. The CWC is the concentration at which these surfactants become superspreaders, as determined by Svitova and others (Langmuir 1998, 14, 5023-5031).

[0011] To help the modified trisiloxane polyalkylene oxides function properly and easily reach the impression material surface, some compositions have been proposed that contain one or more additional surfactants (see, for example, EP 1976479 B1, U.S. Pat. No. 7812065, DE 112007000073, EP 2231102 B1, and U.S. Pat. No. 8466210).

[0012] US Patent Application Publication No. 2008 / 319100 A1 describes a curable polymer selected from the group consisting of organopolysiloxanes that crosslink by addition reactions, organopolysiloxanes that crosslink by condensation reactions, polyethers containing alkoxysilyl radicals that crosslink by condensation reactions, polyethers containing aziridino radicals that crosslink by addition reactions, polyethers containing alkenyl radicals that crosslink by addition reactions, polyethers containing ester radicals of ethylenically unsaturated carboxylic acids that crosslink by radical polymerization reactions, or polyethers, silicones, or rubbers that crosslink by ring-opening metathesis reactions, and the curable polymer contains at least one (poly)alkylene oxide radical. and one silicon-containing nonionic surfactant having a molecular weight of less than 6000 g / mol; and a nonionic fluorosurfactant having at least one partially fluorinated or perfluorohydrocarbon radical connected to a (poly)alkylene oxide radical, a hydrocarbon radical, an aliphatic polyhydroxy radical, or a nitrogen-containing heterocyclic radical by an oxygen atom, an amino group, a keto group, a carboxylic acid ester group, a phosphoric acid ester group, a carboxylic acid amide group, and / or a phosphoric acid amide group, or having at least one partially fluorinated or perfluorohydrocarbon radical and at least one amino oxide radical.

[0013] U.S. Patent Application Publication No. 2019 / 240118 A1 discloses an impression material comprising a catalyst portion and a base portion, wherein the catalyst portion comprises a curable organopolysiloxane polymer, a catalyst, and at least one filler; the base portion comprises a combination of a curable organopolysiloxane polymer, an organopolysiloxane compound capable of crosslinking the curable organopolysiloxane polymer, at least one filler, and a surfactant; the surfactant combination in the base portion comprises a fluoroaliphatic polyoxyethylene surfactant and a monofunctional alcohol alkoxylate surfactant, wherein the fluoroaliphatic polyoxyethylene surfactant is a C6 perfluoroaliphatic chain bonded to a polyoxyethylene fragment giving a total molecular weight range of 400 to 800; and the monofunctional alcohol alkoxylate surfactant is a surfactant of one of the respective formulas set forth in claim 1 of the aforementioned document.

[0014] US Patent Application Publication No. 2011 / 118378 A1 discloses a composition containing a curable polymer selected from the group consisting of organopolysiloxanes that crosslink by addition reactions, organopolysiloxanes that crosslink by condensation reactions, polyethers containing alkoxysilyl groups and that crosslink by condensation reactions, polyethers containing aziridino groups and that crosslink by addition reactions, polyethers containing alkenyl groups and that crosslink by addition reactions, polyethers that contain ester groups of ethylenically unsaturated carboxylic acids and that crosslink by radical polymerization reactions, or polyethers, silicones, or rubbers that crosslink by ring-opening metathesis reactions and also contain at least one nonionic and / or ionic fluorosurfactant as described in claim 1 of the aforementioned document, and also contain at least one nonionic surfactant having a silicon-containing group with a molecular weight of less than 6000 g / mol.

[0015] However, the compositions proposed so far have several drawbacks, among which are cited herein that the concentrations of modified trisiloxane polyalkylene oxide required are relatively high (especially when it is used alone), that the proposed additional surfactant(s) have a negative environmental impact, i.e., are not biodegradable, and that the resulting contact angles are not always satisfactory. Summary of the Invention [Problem to be solved by the invention]

[0016] It is an object of the present invention to provide a hardenable composition for dental impressions, a use of the dental composition, and a method for taking an impression, which are designed to at least partially overcome the above-mentioned drawbacks and which are particularly cheap and easy to make and / or perform. [Means for solving the problem]

[0017] According to the present invention there are provided hardenable compositions for dental impressions, uses of the dental compositions and methods for taking impressions as recited in the following independent claims, preferably as recited in any one of the claims that depend directly or indirectly on the independent claims.

[0018] Unless expressly specified to the contrary, the following terms have the meanings indicated below.

[0019] As used herein, "aliphatic" means a saturated or unsaturated, straight-chain, branched-chain, and / or cyclic, non-aromatic, and unsubstituted (radical) hydrocarbon (unless otherwise specified). Non-limiting examples of aliphatic groups are t-butyl, ethenyl, 1- or 2-propenyl, and cyclohexyl.

[0020] In this specification, C x ~C y refers to a group meaning that it has x to y carbon atoms.

[0021] As used herein, "alkyl" means saturated aliphatic (i.e., an aliphatic group that does not contain double or triple carbon-carbon bonds). Non-limiting examples of alkyl are methyl, n-propyl, t-butyl, and cyclohexyl.

[0022] As used herein, "perfluoro" compounds (PFCs) (or "polyfluoroalkyl" chemicals) are organofluorine compounds (radicals) that contain only carbon-fluorine and C-C bonds (no C-H bonds).

[0023] By "alkoxy" herein is meant an alkyl containing an oxygen bonded to two carbons. DETAILED DESCRIPTION OF THE INVENTION

[0024] According to a first aspect of the present invention, a curable base composition and a compound of formula (I): [ka] (wherein R is each independently a C1-C4 aliphatic group, and (each) R 1 are (independently of each other) C1-C6 aliphatic, and (each) R 2 are (independently) selected from the group consisting of H and C1-C3 aliphatic, and (each) R 3 is (independently of the others) selected from the group consisting of H and C1-C4 aliphatic, x is an integer from 0 to 5, y is an integer from 1 to 10, a is an integer from 1 to 30, and b is an integer from 0 to 5. a surfactant system comprising a first surfactant having (at least one compound having) A hardenable composition for dental impressions is provided, comprising:

[0025] Advantageously, but not necessarily, R is methyl. Additionally or alternatively, (each) R 1 is -C3H6-. Additionally or alternatively, (each) R 2 is -H. Additionally or alternatively, (each) R 3are (independently of one another) selected from the group consisting of —H and methyl, in particular (each) R 3 is methyl. Additionally or alternatively, x is an integer from 0 to 1 (particularly, x is zero). Additionally or alternatively, y is an integer from 1 to 5 (particularly, y is 1 or 2, more particularly, y is 1). Additionally or alternatively, a is an integer from 5 to 20 (particularly, a is 6 to 8, more particularly, a is 7). Additionally or alternatively, b is zero.

[0026] The surfactant system, according to some non-limiting embodiments, has the following formula (II): [ka] (In the formula, R 4 is the following: [ka] is selected from the group consisting of R 5 is the following: [ka] is selected from the group consisting of R 6 is the following: [ka] is selected from the group consisting of In the formula, k, j, z, r, d, and t are each independently an integer of 1 to 10, q is an integer of 1 to 100, Rf is each independently a C1 to C6 fluorine-containing alkyl (particularly perfluoroalkyl), and Rf i are each independently CF3-CF2-CF2-O-CF(CF3)-CH2- and CF3-(CF2) e -(CH2) f wherein e is an integer from 1 to 7 and f is an integer from 1 to 10. The composition further comprises a second surfactant having (at least one compound having)

[0027] It has been experimentally observed that the first surfactant (I) acts synergistically with the second surfactant (II) to enable the composition to have a surprisingly low contact angle (see Examples below). Note that these results were achieved with relatively low concentrations of surfactant. In this regard, it is hypothesized that the second surfactant enhances the migration ability of the first surfactant toward the impression material surface.

[0028] Furthermore, it is important to point out that both the first and second surfactants (especially the second surfactant) are biodegradable, and therefore the present compositions have a significantly more favorable environmental impact than prior art compositions. In particular in this regard, it should be noted that the fluorinated chain of the second surfactant is relatively short.

[0029] Advantageously, but not necessarily, k, j, z, r, d, and t are each independently an integer from 1 to 6, especially from 1 to 3. Additionally or alternatively, q is an integer from 1 to 40, especially from 1 to 20 (more specifically, q is an integer from 1 to 10). Additionally or alternatively, Rf is each independently a C1-C4 fluorine-containing alkyl (especially perfluoroalkyl). Additionally or alternatively, Rf i are each independently selected from the group consisting of CF—CF—CF—O—CF(CF)—CH—, CF—(CF)—(CH)—, and CF—(CF)—(CH)—.

[0030] According to some non-limiting embodiments, R 4 represents structural formula (III), R 5 represents the structural formula (V), and R 6 represents structural formula (VII). Additionally or alternatively, R 5 When represents structural formula (V), R 4 represents structural formula (III), and R 6 represents structural formula (VII). Additionally or alternatively, R 6 represents structural formula (VII), R 5represents the structural formula (V), and R 4 represents structural formula (III).

[0031] In some specific, non-limiting cases, R 4 represents structural formula (III), and R 5 represents the structural formula (V), and R 6 represents structural formula (VII): Compounds of this type are also disclosed in U.S. Patent Application Publication No. 2017 / 0217863.

[0032] According to some non-limiting embodiments, R 4 represents structural formula (IV), R 5 represents structural formula (VI), and R 6 represents structural formula (VIII). Additionally or alternatively, R 5 represents structural formula (VI), R 4 represents structural formula (IV), and R 6 represents structural formula (VIII). Additionally or alternatively, R 6 represents structural formula (VIII), R 5 represents structural formula (VI), and R 4 represents structural formula (IV).

[0033] In some specific, non-limiting cases, R 4 represents structural formula (IV), and R 5 represents structural formula (VI), and R 6 represents structural formula (VIII): Compounds of this type are also disclosed in U.S. Patent Application Publication No. 2013 / 0269568.

[0034] According to specific, non-limiting embodiments, the second surfactant is selected from the group consisting of Tividia FL2500, Tividia FL2300, Tividia FL3000, and combinations thereof. Optionally, the second surfactant is selected from the group consisting of Tividia FL2500, Tividia FL2300, and combinations thereof. In particularly advantageous embodiments, the second surfactant comprises (is) Tividia FL2500.

[0035] Advantageously, but not necessarily, the curable composition comprises from about 0.1% (especially about 1%) to about 7% (especially about 6%) by weight of the first surfactant, based on the total weight of the curable composition.

[0036] Advantageously, but not necessarily, the curable composition comprises from about 0.1% (particularly about 0.3%, more particularly about 0.5%) to about 7% (particularly about 5%, more particularly about 3%) by weight of a second surfactant, based on the total weight of the curable composition.

[0037] Advantageously, but not necessarily, the curable base composition comprises (particularly consists of) a first component comprising (particularly consisting of) at least one curable organopolysiloxane polymer, a second component comprising (particularly consisting of) at least one crosslinker compound capable of crosslinking said organopolysiloxane polymer, and (optionally) a third component comprising (particularly consisting of) a catalyst capable of catalyzing the crosslinking reaction of the first and second components.

[0038] According to some non-limiting embodiments, the third component is a catalyst comprising platinum or tin.

[0039] Advantageously, but not necessarily, the curable composition comprises at least about 0.005% (more particularly about 0.01%), and especially up to about 5% (more particularly about 2%), by weight of catalyst, based on the total weight of the curable composition.

[0040] According to the first category of embodiments (particularly when the third component comprises platinum), the curable composition comprises at least about 0.005% (more particularly about 0.08%), particularly up to about 1% (more particularly about 0.1%) by weight of catalyst, based on the total weight of the curable composition.

[0041] According to the first category of embodiments (particularly when the third component comprises tin), the curable composition comprises at least about 0.5% (more particularly about 0.8%), particularly up to about 3% (more particularly about 2%) by weight of catalyst, based on the total weight of the curable composition.

[0042] According to some non-limiting embodiments, the hardenable base composition also includes one or more fillers (e.g., quartz and / or fumed silica and / or precipitated silica and / or zirconium oxide and / or aluminum silicate and / or aluminum hydroxide and / or calcium silicate and / or calcium carbonate). In some cases, the hardenable composition includes silicon dioxide (e.g., quartz and / or fumed silica).

[0043] In particular, the curable composition comprises from about 25% (particularly about 30%, more particularly about 34%) to about 55% (particularly about 50%) silicon dioxide by weight, based on the total weight of the curable composition.

[0044] According to some non-limiting embodiments, the curable base composition comprises (particularly consists of) a first component comprising (particularly consisting of) an organopolysiloxane having at least two ethylenically unsaturated groups, and a second component (crosslinker) having (in its chain) at least two, particularly at least three, Si—H groups.

[0045] Such organopolysiloxanes advantageously (although not necessarily) have the following formula: CH2=CH-(-SiR A R B O) w -SiR A R B CH=CH2 (In the formula, R A and R B are each independently a substituted or unsubstituted monovalent hydrocarbon (especially aliphatic) radical. It has.

[0046] R Aand R B may contain a double bond.

[0047] R A and R B Examples of groups are methyl, ethyl, phenyl, vinyl, or 3,3,3-trifluoropropyl radicals.

[0048] Preferably, but not necessarily, R A and R B At least one of is methyl.

[0049] The value of the integer w is such that the viscosity of the polymer is 50 cP to 1,000,000 cP at 23° C. The preferred viscosity is 200 to 100,000 cP.

[0050] Silicone oils of different viscosities that do not contain vinyl groups may be present as plasticizers.

[0051] In particular, the third component comprises a hydrosilylation catalyst. The hydrosilylation catalyst may be chloroplatinic acid or a platinum siloxane complex. Alternatively, the catalyst may be a metal such as Rh or Pd.

[0052] The total SiH content in the curable base composition should be such that it ensures complete reaction of all vinyl present in the curable base composition, and the second component (crosslinker) may be present in slight excess. Preferably, but not necessarily, the curable base composition contains a linear or cyclic organopolysiloxane containing a high concentration of vinyl. The presence of such a linear or cyclic organopolysiloxane containing a high concentration of vinyl serves to adjust the reactivity of the platinum present in the catalyst.

[0053] Other materials that may be present in the curable base composition are pigments and colorants, aromatic materials.

[0054] Another possible ingredient is a filler which can be chosen from extending fillers which provide filling, slip and appearance properties, and reinforcing fillers which have a reinforcing function.

[0055] The first or extending filler may be, for example, quartz, calcium carbonate, infusorial earth, iron oxide, aluminum silicate, and alumina. 2 / g, while the second or reinforcing filler has a significantly higher BET surface area and generally consists of silane-treated fumed or precipitated silica.

[0056] In some specific, non-limiting cases, the first component (organopolysiloxane) has a viscosity of about 20 cP to about 50,000 cP (particularly about 500 cP to about 20,000 cP).

[0057] In particular, the second component (crosslinker) comprises (particularly consists of) an organohydrogensiloxane and / or an organohydrogenpolysiloxane. According to some non-limiting embodiments, the second component comprises (particularly consists of) a methylhydrogensiloxane. More particularly, the second component (particularly the methylhydrogensiloxane) has a viscosity of 10 (particularly about 50) to about 200 (particularly about 70) cP (even more particularly about 60 cP). According to specific, non-limiting embodiments, the methylhydrogensiloxane has a SiH content of 1 to 10 mmol / g.

[0058] In particular, the third component is a platinum-containing catalyst. In these cases, advantageously, but not necessarily, the curable composition comprises at least about 0.005% (more particularly about 0.08%), and particularly up to about 1% (more particularly about 0.1%) by weight of catalyst, based on the total weight of the curable composition.

[0059] According to some non-limiting embodiments, the platinum-containing catalyst comprises (is) a Karstedt catalyst.

[0060] Advantageously, but not necessarily, the curable composition comprises at least about 35% (more particularly at least about 40%), and especially up to about 70% (more particularly up to about 65%) by weight of the first component, based on the total weight of the curable composition.

[0061] According to some non-limiting embodiments, the curable composition comprises at least about 35% (more particularly at least about 40%), and particularly up to about 55% (more particularly up to about 50%) by weight of the first component (organopolysiloxane having at least two ethylenically unsaturated groups), based on the total weight of the curable composition.

[0062] Advantageously, but not necessarily, the curable composition comprises at least about 1% (more particularly at least about 5%), and in particular up to about 20% (more particularly up to about 15%) by weight of the second component, based on the total weight of the curable composition.

[0063] According to some non-limiting embodiments, the curable composition comprises at least about 3% (more particularly at least about 5%), and particularly up to about 15% (more particularly up to about 10%) by weight of the second component (organohydrogensiloxane and / or organohydrogenpolysiloxane), based on the total weight of the curable composition.

[0064] The proportions of the different components / ingredients / additives can be varied to achieve the best results.

[0065] According to some non-limiting embodiments, the curable base composition comprises (particularly consists of) a first component comprising (particularly consisting of) at least one hydroxy-terminated organopolysiloxane and a second component (crosslinker) comprising (particularly consisting of) an alkoxysilane.

[0066] Examples of hydroxy-terminated organopolysiloxanes (ie organopolysiloxanes that can be cured by condensation reactions) are known, for example, from DE 41 37 698 A1.

[0067] Typically, the hydroxy-terminated organopolysiloxane (i.e., an organopolysiloxane that can be cured by a condensation reaction) is represented by the following formula (XVI): HO-SiR * 2-B1-SiR * 2-OH (XVI) (In the formula, R * are each independently a C1-C4 aliphatic (especially alkyl, more particularly methyl) group, and B1 is of the formula -O-(SiR'-O) m2 - (wherein R' are each independently a (particularly C1-C6, more particularly C1-C4) alkyl, alkenyl, alkynyl, cycloalkyl, aryl and / or aralkyl radical, which may be substituted, and m2 is an integer of 10 to 6000, preferably 20 to 2000). According to some non-limiting examples, R' are each independently of the other (particularly C1-C6, more particularly C1-C4) alkyl (such as methyl, ethyl, n-propyl, isopropyl, or n-butyl).

[0068] Typically, the alkoxysilanes have the following formulae (XVII), (XVIII) and (XIX): (R”O) m3 -SiR” 3-m3 -B2-SiR” 3-m3 -(OR”) m3 (XVII) SiR” m4 (OR ** ) 4-m4 (XVIII) [ka] (wherein R" is each independently of the others (particularly C1-C6, more particularly C1-C4) alkyl, alkenyl, alkynyl, cycloalkyl, aryl and / or aralkyl, which may be substituted; R **are each independently (particularly C1-C6, more particularly C1-C4) alkyl, alkenyl, alkynyl, cycloalkyl, aryl and / or aralkyl (which may be substituted); m3 is an integer of 1 to 3; m4 is an integer of 0 to 2; B2 is a group of the formula -O-(SiR 1t 2-O) m5 represents a radical having R 1t each independently represents (particularly C1 to C6, more particularly C1 to C4) alkyl, alkenyl, alkynyl, cycloalkyl, aryl and / or aralkyl (which may be substituted), and m5 is an integer of 10 to 6000, preferably 1 to 2000 (particularly 1 to 100, more particularly 50 to 70). It is a compound having one of the following:

[0069] By way of some non-limiting examples, R ** are each independently (particularly C1 to C6, more particularly C1 to C4) alkyl (such as methyl, ethyl, n-propyl, isopropyl or n-butyl).

[0070] According to some non-limiting examples, R″ are each independently of one another (particularly C1-C6, more particularly C1-C4) alkyl (such as methyl, ethyl, n-propyl, isopropyl, or n-butyl).

[0071] By way of some non-limiting examples, R 1t are each independently (particularly C1 to C6, more particularly C1 to C4) alkyl (such as methyl, ethyl, n-propyl, isopropyl or n-butyl).

[0072] In particular, the third component is a tin-containing catalyst. In these cases, advantageously, but not necessarily, the curable composition comprises at least about 0.5% (more particularly about 0.8%), and especially up to about 3% (more particularly about 2%) by weight of catalyst, based on the total weight of the curable composition.

[0073] According to some non-limiting embodiments, the tin-containing catalyst comprises (is) dibutyltin dilaurate (IUPAC name: [dibutyl(dodecanoyloxy)stannyl]dodecanoate), dibutyltin diacetate (IUPAC name: [acetyloxy(dibutyl)stannyl]acetate), dioctyltin oxide (IUPAC name: dioctyl(oxo)tin—CAS number 870-08-6), and / or tin(II) octoate (IUPAC name: lead(2+) octoate). In some particular cases, the tin-containing catalyst comprises (is) dioctyltin oxide.

[0074] Advantageously, but not necessarily, the first component (hydroxy-terminated organopolysiloxane) has a viscosity of from about 500 cP to about 80,000 cP (particularly from 1,000 cP to about 20,000 cP).

[0075] Advantageously, but not necessarily, the second component (alkoxysilane) comprises (is) methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, tetrakis-(butoxy-ethoxy)silane ((CH3-(CH2)3-O-(CH2)2-O)4-Si), methyltriacetoxysilane (CAS number: 4253-34-3).

[0076] According to some non-limiting embodiments, the curable composition comprises about 1% (particularly about 2%) to about 5% (particularly about 4%) by weight of the second component (alkoxysilane), based on the total weight of the curable composition.

[0077] All of the above mentioned components should be combined together in a specific way to achieve an impression-taking material with the required rheological, mechanical and biocompatible properties.

[0078] According to a further non-limiting embodiment, the second surfactant has the following formula (IX): [ka] (In the formula, Rf ii represents a C1-C6 fluorine-containing alkyl, and R 7 represents a C1-C4 alkyl, Ra represents a C1-C3 alkyl, Rb represents a C1-C3 alkyl, Rc is selected from the group consisting of a C1-C6 aliphatic (particularly alkyl) and a C1-C6 alkoxy, Rp represents a C1-C6 alkyl, ax is an integer of 1 to 10, ay is an integer of 1 to 10, aa is an integer of 0 to 20, ab is an integer of 0 to 20, ac is an integer of 1 to 20, ae is an integer of 0 to 1, when Rc is alkoxy, ae is 1, and when Rc is alkyl, ae is zero. (It is at least one compound having)

[0079] More particularly, when Rc is alkoxy, it represents the formula -Rq-O-, where Rq represents C1-C6 alkyl (in particular is the same as Rp).

[0080] It has been experimentally observed that the first surfactant (I) acts synergistically with the second surfactant (IX), allowing the composition to have a surprisingly lower contact angle (see Examples below). Note that these results are achieved with relatively low concentrations of surfactant. In this regard, it was hypothesized that the second surfactant enhances the migration ability of the first surfactant toward the impression material surface.

[0081] Furthermore, it is important to point out that both the first and second surfactants (especially the second surfactant) are biodegradable, and therefore the present compositions have a significantly more favorable environmental impact over prior art compositions.

[0082] Advantageously, but not necessarily, Rf ii represents a C1-C4 (particularly C3-C4, more particularly C4) fluorine-containing (particularly perfluoro) alkyl. Additionally or alternatively, R 7represents C1-C2 alkyl. Additionally or alternatively, Ra represents C2 alkyl (particularly ethyl). Additionally or alternatively, Rb represents C2 alkyl (particularly ethyl). Additionally or alternatively, Rc is selected from the group consisting of C3-C5 alkyl, C2-C4 alkoxy. Additionally or alternatively, ax is an integer from 1 to 6. Additionally or alternatively, ay is an integer from 1 to 6. Additionally or alternatively, aa is an integer from 0 to 12 and ab is an integer from 0 to 12. Additionally or alternatively, ac is an integer from 1 to 16.

[0083] According to some non-limiting embodiments, Rf ii represents a C2-C4 fluorine-containing (particularly perfluoro) alkyl.

[0084] Additionally or alternatively, R 7 represents C1-C2 alkyl. Additionally or alternatively, ax is an integer from 1 (particularly 4) to 6 (particularly 5). Additionally or alternatively, ay is an integer from 1 (particularly 4) to 6 (particularly 5).

[0085] According to some non-limiting embodiments, aa is zero. Additionally or alternatively, ab is zero. Additionally or alternatively, ac is 1. Additionally or alternatively, Rc represents C3-C5 alkyl. Additionally or alternatively, ae is zero.

[0086] According to some non-limiting embodiments, ax+ay is 4 (particularly 5) to 8 (particularly 7). Additionally or alternatively, ac is 10 (particularly 14) to 20 (particularly 18), and in some particular cases, ac is 16. Additionally or alternatively, Rc is C-Calkoxy (more particularly, —CH—CH(CH)—O—).

[0087] Specifically, in formula (IX), the sum of ax and ay is an integer of 4 to 6.

[0088] According to some specific, non-limiting embodiments, the second surfactant is: [ka] (wherein the sum of ax and ay is an integer of 4 to 6) The compound comprises (is) (at least one) compound having a formula selected from the group consisting of:

[0089] In some non-limiting cases, the second surfactant comprises (is) (at least one) compound having a formula selected from the group consisting of (XIII) and (XIV). In more specific non-limiting cases, the second surfactant comprises (is) (at least one) compound having formula (XIII).

[0090] In some particular cases, the second surfactant has the following formula: [ka] and more particularly the second surfactant is Polyfox PF 159 (Omnova Solutions™).

[0091] Additionally or alternatively, the second surfactant comprises (is) the surfactant of Example 3 reported below (Polyfox PF 7002).

[0092] Advantageously, but not necessarily (particularly when the second surfactant has formula (IX)), the curable composition comprises: [ka] (wherein xx is an integer of 2 to 10, m is an integer of 1 to 20, n is an integer of 0 to 200 (particularly up to 100), and each Rd is independently selected from the group consisting of -F and -CF3.) The fluoro compound is (has) at least one compound having a formula selected from the group consisting of:

[0093] It has been experimentally observed that very low concentrations of the fluorocompound act synergistically with the first surfactant (I) and the second surfactant (IX) to enable the present composition to have a surprisingly low contact angle (see Examples below).

[0094] Specifically, up to two Rd's are each -CF3, and the remaining Rd's are each -F. More specifically, the two -CF3's are in meta positions relative to each other.

[0095] According to a non-limiting embodiment, the fluoro compound is (has) at least one compound having a formula selected from the group consisting of formula (XI) and formula (XII).

[0096] Additionally or alternatively, the fluoro compound is (has) at least one compound having formula (X):

[0097] Advantageously, but not necessarily, the curable composition comprises from 0.1% to about 3% (especially about 1.5%) by weight of a fluoro compound, based on the total weight of the curable composition.

[0098] All of the above mentioned components should be combined together in a specific way to achieve an impression-taking material with the required rheological, mechanical and biocompatible properties.

[0099] According to a second aspect of the present invention there is provided the use of a hardenable composition according to the first aspect of the present invention for taking an impression of at least part of a mouth, in particular the use comprising contacting the hardenable composition with at least part of the mouth.

[0100] According to a third aspect of the present invention there is provided a method of taking an impression comprising contacting at least a part of a mouth with the hardenable composition according to the first aspect of the present invention as described above.

[0101] Viscosity measurements are believed to be performed according to the following: Viscosity is measured and measured using a Brookfield Viscometer DVII. The measurements are performed at 23°C and a spindle speed of 20 rpm. A ULA spindle is used and was used for viscosities ranging from 20 to 200 cP. Spindle SC4-21 is used and was used for viscosities ranging from 500 to 1000 cP. Spindle SC4-29 is used and was used for viscosities ranging from 2000 to 20000 cP. Spindle SC4-29 is used and was used for viscosities ranging from 50000 to 100000 cP.

[0102] Viscosity measurements were and are carried out in accordance with the content provided by the DIN EN ISO 3219:1993 standard (in particular on the basis of DIN 53019-1).

[0103] Unless expressly indicated to the contrary, the entire contents of the references (articles, books, patent applications, etc.) cited herein are incorporated by reference, and the cited references are specifically incorporated herein by reference.

[0104] Further features of the present invention will become apparent from the following description of examples, which are given by way of illustration and not of limitation. [Example]

[0105] Example 1 This example discloses the procedure followed for contact angle measurements (sessile drop method).

[0106] A drop of distilled water was placed on a silicone surface (50 μm thick) cured under the following environmental conditions: temperature of 23±1° C. and relative humidity of 50±10%.

[0107] A Kruss DSA30 was used to record videos and capture droplet deposition.

[0108] Measurements were taken 5 seconds and 30 seconds after deposition.

[0109] The compositions tested in Examples 2-15 had the following ingredients: [Table 1]

[0110] The polyvinylsiloxanes had the following viscosities: 200 cP (15% base + catalyst, vinyl content 0.28 mmol / g), 1000 cP (5% base + catalyst, vinyl content 0.127 mmol / g), 2000 cP (20% base + catalyst, vinyl content 0.097 mmol / g), 20000 cP (5% base + catalyst, vinyl content 0.04 mmol / g).

[0111] The methylhydrogen siloxane had a viscosity of 60 cP and a SiH content of 1.7 mmol / g.

[0112] The platinum catalyst was Karstedt's catalyst (CAS number 68478-92-2).

[0113] The ingredients were mixed using the following operating instructions.

[0114] The base was first prepared using a vertical mixer equipped with a Cowles (saw blade impeller): the pigment was dispersed in the polyvinylsiloxane for 5 minutes, after which the quartz and fumed silica were added and mixed for 20 minutes. The flavoring was also added during this final step and mixed for 10 minutes.

[0115] The catalyst was prepared using a vertical mixer equipped with a Cowles (saw blade impeller): the pigment was dispersed in the methylhydrogen siloxane for 5 minutes, then the quartz and fumed silica were added and mixed for 20 minutes. During the final step, the platinum catalyst was added and mixed for 10 minutes.

[0116] The surfactant was then added to the above mixture using a disperser equipped with a Cowles (saw blade impeller) and mixed for a total of 15 minutes.

[0117] Between 3 weight phr (parts per million by weight of rubber / resin) and 6.4 weight phr of surfactant was added to both mixtures (3 to 6.4 weight phr of s and t). The phr should be considered relative to the weight of all other components / ingredients of the composition / mixture. For example, if the surfactant has 6.4 weight phr, the total weight of the composition would be 106.4, and the ratio of the weight of surfactant to the total weight of the composition would be 6.4 / 106.4 (corresponding to approximately 6 wt %).

[0118] The base and catalyst obtained after the addition of the surfactant were then introduced into a 50 ml cartridge (25 mL of base and 25 mL of catalyst, 1:1), whereby mixing was carried out using a dispenser and mixing tip for each example.

[0119] The compositions tested in Examples 16-19 had the following ingredients: [Table 2]

[0120] The hydroxy-terminated polysiloxanes had the following viscosities: 2000 cP (25% based on base), 5000 cP (35.5% based on base).

[0121] The silicon dioxide was quartz and fumed silica.

[0122] The alkoxysilane was tetrakis-(butoxy-ethoxy)silane-(CH3-(CH2)3-O-(CH2)2-O)4-Si.

[0123] The tin catalyst was dioctyltin oxide.

[0124] The ingredients were mixed using the following operating instructions.

[0125] The base was first prepared using a vertical mixer equipped with a Cowles: the pigment was dispersed in the hydroxy-terminated polysiloxane for 5 minutes, then the quartz and fumed silica were added and mixed for 20 minutes. During this final step, the flavoring was added and mixed for 10 minutes (the last 5 minutes under vacuum).

[0126] The catalyst was then prepared in the following manner: the hydrocarbon was melted in a reactor at 90° C. and mixed with the pigment for a total period of 3 hours, then the alkoxysilane and flavoring were added and mixed for 1 hour.

[0127] The surfactant was then added to the mixture using a Cowles-equipped disperser and mixed for a total of 15 minutes.

[0128] The surfactants were added in a proportion of 1 to 2.5 weight phr (1 to 2.5 weight phr of s and t).

[0129] Finally, for each example, the base was introduced into a 140 ml tube and the catalyst into a 60 ml tube.

[0130] Mixing was done by hand using a spatula and pouring in the base and catalyst in a weight ratio of 10:0.32 for each example.

[0131] Example 2 (Comparative Example) The surfactant has the following formula: [ka] (Wherein R and R 3 is -CH3 and R 1 is -C3H6- and R 2 was hydrogen, x was 0 or 1, y was 1 or 2, a was about 7, and b was 0. The contact angle was 33.7° at 5 seconds and 15.5° at 30 seconds.

[0132] This example was used as a reference for Examples 3-16.

[0133] Example 3 The surfactants were 3 phr by weight of Silwet L77 and 1 phr by weight of Polyfox PF 7002 (Omnova Solutions™), whose structure was: [ka]

[0134] The contact angle was 37.1° at 5 seconds and 11.5° at 30 seconds.

[0135] Performance improved over the reference (Example 2) at 5 seconds, although there was a slight decrease in contact angle at 30 seconds.

[0136] Example 4 The surfactants were 3 phr by weight of Silwet L77, 1 phr by weight of Polyfox PF 7002, and 1 phr by weight of Fluorosil D2 (Siltech™), whose structure was the following, where x=3, m was 0-20, and n was 1-200: [ka]

[0137] The contact angle was 22.3° at 5 seconds and 10.3° at 30 seconds.

[0138] The composition had a better contact angle than Example 3, in which only Polyfox PF 7002 and Silwet L77 were present.

[0139] Example 5 The surfactants were 3 wt phr Silwet L77, 1 wt phr Polyfox PF 7002, and 0.5 wt phr perfluorodecalin, the structure of which was: [ka]

[0140] The contact angle was 24.9° at 5 seconds and 6.9° at 30 seconds.

[0141] The fluorinated compounds provided the composition with better contact angles than those of Example 3, where only Polyfox PF 7002 and Silwet L77 were present.

[0142] Example 6 The surfactants were 3 wt phr Silwet L77, 1 wt phr Polyfox PF 7002, and 0.2 wt phr perfluoro-1,3-dimethylcyclohexane, whose structure was: [ka]

[0143] The contact angle was 27.5° at 5 seconds and 8.3° at 30 seconds.

[0144] The composition had a better contact angle than that of Example 3, in which only Polyfox PF 7002 and Silwet L77 were present.

[0145] Example 7 The surfactants were 3 wt phr Silwet L77, 1 wt phr Polyfox PF 7002, and 0.5 wt phr perfluoro-1,3-dimethylcyclohexane (see above).

[0146] The contact angle was 24.6° at 5 seconds and 7.8° at 30 seconds.

[0147] The composition had a better contact angle than that of Example 3, in which only Polyfox PF 7002 and Silwet L77 were present. Increasing the amount of perfluoro-1,3-dimethylcyclohexane did not have a significant effect on the reduction in contact angle.

[0148] Example 8 The surfactants were 3 wt phr Silwet L77, 1 wt phr Polyfox PF 7002, and 0.8 wt phr perfluoro-1,3-dimethylcyclohexane (see above).

[0149] The contact angle was 25.4° at 5 seconds and 7.8° at 30 seconds.

[0150] The composition had a better contact angle than that of Example 3, in which only Polyfox PF 7002 and Silwet L77 were present. Increasing the amount of perfluoro-1,3-dimethylcyclohexane did not have a significant effect on the reduction in contact angle.

[0151] Example 9 The surfactants were 3 phr by weight of Silwet L77 and 1 phr by weight of Tivida FL2500 (Merck™), whose structure is as follows: where k, j, z, r, d, and t are each independently an integer from 1 to 10, and Rf is each independently a C1-C6 fluorine-containing alkyl. [ka]

[0152] The contact angle was 21.3° at 5 seconds and 1.7° at 30 seconds. The performance was better than the reference (Example 2), especially at 30 seconds.

[0153] Example 10 The surfactants were 3 weight phr of Silwet L77 and 3.4 weight phr of Tivida FL2500 (Merck™), whose structure is as follows: where k, j, z, r, d, and t are each independently an integer from 1 to 10, and Rf is each independently a C1-C6 fluorine-containing alkyl. [ka]

[0154] The contact angle was 6.5° at 5 seconds and 1.4° at 30 seconds. Performance was significantly better than the reference (Example 2) even at 5 seconds.

[0155] Example 11 The surfactants were 3 weight phr of Silwet L77 and 3.4 weight phr of Tivida FL2300 (Merck™), whose structure is as follows: where k, j, z, r, d, and t are each independently an integer from 1 to 10, and Rf is each independently a C1-C6 fluorine-containing alkyl. [ka]

[0156] The contact angle was 29.1° at 5 seconds and 8.7° at 30 seconds. The performance was better than the reference (Example 2).

[0157] Example 12 The surfactants were 3 phr by weight of Silwet L77 and 1 phr by weight of Tivida FL3000 (Merck™), whose structure is shown below, where q is an integer from 1 to 20, and Rf i are each independently CF3-CF2-CF2-O-CF(CF3)-CH2- and CF3-(CF2) e -(CH2) f -, wherein e is an integer from 1 to 7, and f is an integer from 1 to 10. [ka]

[0158] The contact angle was 9.4° at 5 seconds and 6.4° at 30 seconds. Performance was significantly better than the reference (Example 2) even at 5 seconds.

[0159] Example 13 (Comparative Example) The surfactants were 3 phr by weight of Silwet L77 and 1 phr by weight of FluorN 561 (Cytonix™), whose structure contains four groups: two perfluor and two polyethylene glycol, pendant from a polypropylene glycol-based matrix.

[0160] The contact angle was 46° at 5 seconds and 18.4° at 30 seconds, a performance worse than the reference (Example 2).

[0161] Example 14 (Comparative Example) The surfactants were 3 phr by weight of Silwet L77 and 1 phr by weight of FluorN 562 (Cytonix™), whose structure contains four groups: one perfluoro and three polyethylene glycol groups, pendant from a polypropylene glycol-based matrix.

[0162] The contact angle was 42.1° at 5 seconds and 16.4° at 30 seconds, a performance worse than the reference (Example 2).

[0163] Example 15 (Comparative Example) The surfactants were 3 phr by weight of Silwet L77 and 1 phr by weight of FluorN 2900 (Cytonix), whose structure was a high molecular weight, glycol-terminated perfluoroethylene.

[0164] The contact angle was 29.5° at 5 seconds and 13.1° at 30 seconds. The performance was not better than the reference (Example 2).

[0165] Example 16 (Comparative Example) The surfactant was 1 phr by weight of Silwet L77 (Momentive) having the following formula: [ka] (Wherein R and R 3 is -CH3 and R 1 is -C3H6- and R2 was hydrogen, x was 0 or 1, y was 1 or 2, a was about 7, and b was 0. The contact angle was 52.9° at 5 seconds and 35.8° at 30 seconds.

[0166] This example was used as a reference for Examples 17-19.

[0167] Example 17 The surfactants were 1 phr by weight of Silwet L77 and 1 phr by weight of Tivida FL3000 (Merck), whose structure is shown below, where q is an integer from 1 to 100, and Rf i are each independently CF3-CF2-CF2-O-CF(CF3)-CH2- and CF3-(CF2) e -(CH2) f -, wherein e is an integer from 1 to 7, and m is an integer from 1 to 10. [ka]

[0168] The contact angle was 25.4° at 5 seconds and 16.4° at 30 seconds. Performance was significantly better than the reference (Example 16), even at 5 seconds.

[0169] Example 18 (Comparative Example) The surfactants were 1 phr by weight of Silwet L77 and 1 phr by weight of Polyfox PF 7002 (Omnova Solutions), the structure of which was: [ka]

[0170] The contact angle was 52.1° at 5 seconds and 31.5° at 30 seconds.

[0171] The performance was slightly better than the reference (Example 16).

[0172] Example 19 The surfactants were 1 phr by weight of Silwet L77, 1 phr by weight of Polyfox PF 7002, and 0.5 phr by weight of perfluorodecalin, the structure of which was: [ka]

[0173] The contact angle was 27.2° at 5 seconds and 19.5° at 30 seconds.

[0174] The fluorinated compounds gave the composition a better contact angle than Example 18, in which only Polyfox PF 7002 and Silwet L77 were present.

[0175] While the principles of the present invention have been explained in connection with specific embodiments, it will be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. It is therefore to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims. The scope of the present invention is limited only by the appended claims.

Claims

1. a curable base composition; and 1. A surfactant system comprising a surfactant of the following formula (I): 【Chemistry 1】 (wherein each R is independently C １ ~C ４ is aliphatic, and each R １ is independent of others １ ~C ６ is aliphatic, and each R ２ are independently H and C １ ~C ３ aliphatic, and each R ３ are independently H and C １ ~C ４ aliphatic, x is an integer from 0 to 5, y is an integer from 1 to 10, a is an integer from 1 to 30, and b is an integer from 0 to 5. a first surfactant which is at least one compound having the formula: Formula (II): 【Chemistry 2】 (In the formula, R ４ is the following: 【Transformation 3】 is selected from the group consisting of R ５ is the following: 【Chemistry 4】 is selected from the group consisting of R ６ is the following: 【Transformation 5】 is selected from the group consisting of In the formula, k, j, z, r, d, and t are each independently an integer of 1 to 10, q is an integer of 1 to 100, and Rf is each independently C １ ~C ６ is a fluorine-containing alkyl, and Rf ｉ are each independently CF ３ -CF ２ -CF ２ -O-CF(CF ３ )-CH ２ - and CF ３ -(CF ２ ) ｅ - (CH ２ ) ｆ wherein e is an integer from 1 to 7 and f is an integer from 1 to 10. a second surfactant which is at least one compound having the formula a surfactant system comprising 1. A hardenable composition for dental impressions comprising:

2. each R is methyl; １ Ga-C ３ H ６ - and each R ２ is H, and each R ３ is independently selected from the group consisting of H and methyl, x is an integer from 0 to 1, y is an integer from 1 to 5, a is an integer from 5 to 20, and b is zero; k, j, z, r, d, and t are each independently 1 to 6, q is 1 to 40, and Rf is each independently C １ ~C ４ is a fluorine-containing alkyl, and Rf ｉ are each independently of each other and CF ３ -CF ２ -CF ２ -O-CF(CF ３ )-CH ２ -, CF ３ -(CF ２ ) ２ - (CH ２ ) -, and CF ３ -(CF ２ )-(CH ２ )-selected from the group consisting of The curable composition of claim 1.

3. R ４ but below: 【Transformation 6】 represents R ５ but below: 【Transformation 7】 and R ６ but below: 【Transformation 8】 3. The curable composition according to claim 1, wherein

4. R ４ but below: 【Chemistry 9】 represents R ５ but below: 【Chemistry 10】 and R ６ but below: 【Chemistry 11】 3. The curable composition according to claim 1, wherein

5. a curable base composition; and 1. A surfactant system comprising a surfactant of the following formula (I): 【Chemistry 12】 (wherein each R is independently C １ ~C ４ is aliphatic, and each R １ is independent of others １ ~C ６ is aliphatic, and each R ２ are independently H and C １ ~C ３ aliphatic, and each R ３ are independently H and C １ ~C ４ aliphatic, x is an integer from 0 to 5, y is an integer from 1 to 10, a is an integer from 1 to 30, and b is an integer from 0 to 5. a first surfactant which is at least one compound having the formula: The following formula (IX): 【Chemistry 13】 (wherein, Rf ｉｉ is C １ ~C ６ represents a fluorine-containing alkyl, and R ７ is C １ ~C ４ represents alkyl, and Ra is C １ ~C ３ alkyl, and Rb is C １ ~C ３ represents alkyl, and Rc is C １ ~C ６ aliphatic, C １ ~C ６ alkoxy, and Rp is C １ ~C ６ ax is an integer of 1 to 10, ay is an integer of 1 to 10, aa is an integer of 0 to 20, ab is an integer of 0 to 20, ac is an integer of 1 to 20, ae is an integer of 0 to 1, when Rc is alkoxy, ae is 1, when Rc is alkyl, ae is zero a second surfactant which is at least one compound having the formula a surfactant system comprising 1. A hardenable composition for dental impressions comprising:

6. Rf ｉｉ is C １ ~C ４ represents a fluorine-containing alkyl, and R ７ is C １ ~C ２ R represents alkyl, R represents ethyl, R represents ethyl, and R represents C ３ ~C ５ Alkyl, C ２ ~C ４ 6. The curable composition according to claim 5, wherein ax is an integer of 1 to 6, ay is an integer of 1 to 6, aa is an integer of 0 to 12, ab is an integer of 0 to 12, and ac is an integer of 1 to 16.

7. Rf ｉｉ is C ２ ~C ４ represents a fluorine-containing alkyl, and R ７ is C １ ~C ２ represents alkyl, and Rc is C ３ ~C ５ The curable composition according to claim 5 or 6, wherein ax represents an integer of 1 to 5, ay represents an integer of 1 to 5, aa is zero, ab is zero, ac is 1, and ae is zero.

8. below: 【Chemistry 14】 (wherein xx is an integer of 2 to 10, m is an integer of 1 to 20, n is an integer of 0 to 200, and each Rd is independently -F, -CF ３ selected from the group consisting of The curable composition of any one of claims 5 to 7, comprising a fluoro compound, which is at least one compound having a formula selected from the group consisting of:

9. The fluoro compound is at least one compound having a formula selected from the group consisting of formula (XI) and formula (XII), wherein up to two Rd are each —CF ３ and each remaining Rd is —F.

10. 10. The curable composition according to claim 1, wherein the curable base composition comprises: a first component comprising a curable organopolysiloxane polymer; a second component comprising a crosslinker compound capable of crosslinking the organopolysiloxane polymer; and a third component comprising a catalyst capable of catalyzing a crosslinking reaction of the first component and the second component, wherein the third component is a catalyst comprising platinum or tin.

11. 11. The curable composition of claim 10, wherein the curable base composition comprises a first component comprising an organopolysiloxane having at least two ethylenically unsaturated groups, a second component comprising an organohydrogensiloxane and / or organopolysiloxane having Si—H groups, and the third component is a catalyst comprising platinum.

12. 11. The curable composition of claim 10, wherein the curable base composition comprises a first component comprising a hydroxy-terminated polysiloxane, a second component comprising an alkoxysilane, and the third component is a catalyst comprising tin.

13. 13. The curable composition of any one of claims 1 to 12, comprising 0.1% to 7% by weight of the first surfactant, based on about the total weight of the curable composition, and 0.1% to 7% by weight of the second surfactant, based on the total weight of the curable composition.

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