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    公开号:BR112013019702B1
    申请号:R112013019702-1
    申请日:2012-02-08
    公开日:2018-05-22
    发明作者:D. Joly Guy；R. Krepski Larry；N. Gaddam Babu；S. Abuelyaman Ahmed；D. Craig Bradley；D. Dunbar Timothy；Cao Chuntao；D. Oxman Joel；Falsafi Afshin；H. Moser William；T. Bui Hoa
    申请人:3M Innovatative Properties Company；
    IPC主号:
    专利说明:

    (54) Title: DENTAL COMPOSITIONS UNDERSTANDING ETHYLENICALLY UNSATURATED ADDITION-FRAGMENTATION AGENT.
    (51) Int.CI .: A61K 6/083 (30) Unionist Priority: 08/08/2011 US 61 / 521,134, 02/15/2011 US 61 / 443,218 (73) Holder (s): 3M INNOVATATIVE PROPERTIES COMPANY ( 72) Inventor (s): GUY D. JOLY; LARRY R. KREPSKI; BABU N. GADDAM; AHMED S.
    ABUELYAMAN; BRADLEY D. CRAIG; TIMOTHY D. DUNBAR; CHUNTAO CAO; JOEL D. OXMAN; AFSHIN FALSAFI; WILLIAM H. MOSER; HOAT. BUI
    1/54 “DENTAL COMPOSITIONS UNDERSTANDING ETHYLENICALLY Unsaturated Addition-FRAGMENTATION AGENT”
    summary
    Although various hardenable dental compositions have been described, the industry would find advantage in compositions having improved properties such as reduced stress deflection and / or reduced shrinkage while maintaining sufficient mechanical properties and curing depth.
    In one embodiment, a dental composition is described comprising an addition-fragmentation agent comprising at least one ethylenically unsaturated end group and a main chain unit comprising an α, β-unsaturated carbonyl; at least one monomer comprising at least two ethylenically unsaturated groups; and inorganic oxide charge. The addition-fragmentation agent is preferably radically freely cleavable. The addition-fragmentation agent preferably comprises at least two ethylenically unsaturated end groups, such as (meth) acrylate groups. In some embodiments, the addition-fragmentation agent has the formula:
    in which
    R 1 , R 2 and R 3 are each independently Zm-Q-, a (hetero) alkyl group or a (hetero) aryl group with the proviso that at least one of R 1 , R 2 and R 3 is Zm- Q-;
    Q is a linking group that has a valence of m +1;
    Z is an ethylenically unsaturated polymerizable group; m is 1 to 6;
    each X 1 is independently -O- or -NR 4 -, where R 4 is H or C1-C4 alkyl; and n is 0 or 1.
    In another embodiment, a dental article comprising a curable dental composition comprising an addition-fragmentation agent as described herein is at least partially cured.
    In other embodiments, methods for treating a dental surface are described. In one embodiment, the method comprises providing a curable dental composition comprising an addition-fragmentation agent as described herein; positioning the dental composition on a dental surface within a subject's mouth; and hardening the curable dental composition. In another embodiment, the method comprises providing an at least partially hardened dental article comprising an agent
    2/54 addition-fragmentation as described herein, and adhere the dental article to a dental surface within a subject's mouth.
    Brief Description of Drawings
    Figure 1 depicts a machined aluminum block used as a sample holder for a curable composition during the stress deflection test.
    Figure 2 shows a voltage deflection tester.
    Detailed Description
    For use in the present invention, "dental composition" refers to a material, optionally comprising filler, capable of adhering to or bonding to a buccal surface. A curable dental composition can be used to bond a dental article to a dental structure, form a coating (for example a sealant or varnish) on a dental surface, be used as a restorative that is positioned directly inside the mouth and cured locally, or alternatively be used to manufacture a prosthesis outside the mouth that is subsequently adhered into the mouth.
    Curable dental compositions include, for example, adhesives (for example dental and / or orthodontic adhesives), cements (for example resin-modified glass ionomer cements, and / or orthodontic cements), primers (for example orthodontic primers), linings ( liners) (applied at the base of a cavity to reduce tooth sensitivity), coatings such as sealants (for example, pit and fissure), and varnishes; and resin restorers (also called direct composites) such as dental fillings, as well as crowns, bridges, and dental implant articles. Highly loaded dental compositions are also used for rough blocks for milling prostheses (mill blanks), from which a crown can be machined. A composite is a highly loaded paste designed to be suitable for filling defects in dental structure. Dental cements are somewhat less loaded and with less viscous materials than composites, and typically act as a bonding agent for additional materials, such as inlays, onlays and the like, or act as filler material by itself, if applied and cured in the layers. Dental cements are also used to permanently bond dental restorations such as a crown or bridge to a dental surface or implant abutment.
    For use in the present invention;
    “Dental article” refers to an article that can be attached (for example bonded) to a dental structure or dental implant. Dental articles include, for example, crowns, bridges, veneers, inlays, onlays, fillings, orthodontic appliances and devices.
    “Orthodontic appliance” refers to any device intended to be attached to a dental structure, including, but not limited to, orthodontic bracket supports, mouth tubes, lingual retainers, orthodontic bands, bite openers,
    3/54 buttons, and handles. The device has a base for receiving the adhesive and can be a flange made of metal, plastic, ceramic, or combinations thereof. Alternatively, the base may be a custom base formed from cured adhesive layer (s) (i.e., single layer or multilayer adhesives).
    “Oral surface” refers to a soft or hard surface in the oral environment. Hard surfaces typically include dental structure including, for example, natural and artificial dental surfaces, bone and the like.
    "Curable" and "curable" is descriptive of a material or composition that can be cured (for example polymerized (a) or cross-linked (a)) by heating to induce polymerization and / or cross-linking; irradiation with actinic irradiation to induce polymerization and / or cross-linking; and / or by mixing one or more components to induce polymerization and / or crosslinking. Mixing ”can be carried out, for example, by combining two or more parts and admistan to form a homogeneous composition. Alternatively, two or more parts can be provided as separate layers that intermix (for example spontaneously or by applying shear stress) at the interface to initiate polymerization.
    "Hardened" refers to a material or composition that has been cured (for example polymerized or cross-linked).
    “Hardener” refers to something that initiates the hardening of a resin. A hardener can include, for example, a polymerization initiator system, a photoinitiator system, a thermal initiator system and / or a redox initiator system.
    “(Met) acrylate” is an abbreviated reference to acrylate, methacrylate or combinations thereof; “(Met) acrylic” is an abbreviated reference to acrylic, methacrylic or their combinations; and “(met) acryl” is an abbreviated reference to acryl, methacryl or combinations thereof.
    “Acryloyl” is used in a general sense and means not only derivatives of acrylic acid, but also amine, and derivatives of alcohol, respectively;
    "(Meth) acryloyl" includes both the acryloyl and methacryloyl groups; that is, it is inclusive of both esters and amides.
    "Alkyl" includes straight chain, branched and cyclic alkyl groups and includes both unsubstituted and substituted alkyl groups. Unless otherwise noted, alkyl groups typically contain 1 to 20 carbon atoms. Examples of "alkyl" for use in the present invention include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n- heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, and norbornyl, and the like. Except where otherwise specified, alkyl groups may be mono or polyvalent, i.e., monovalent alkyl or polyvalent alkylene.
    "Heteroalkyl" includes straight chain, branched and cyclic alkyl groups with one or more heteroatoms selected independently from S, O and N with non-alkyl groups
    4/54 replaced and replaced. Unless otherwise noted, heteroalkyl groups typically contain 1 to 20 carbon atoms. "Heteroalkyl is a subset of" hydrocarbyl containing one or more S, N, O, P or Si atoms "described below. Examples of "heteroalkyl" for use in the present invention include, but are not limited to, methoxy, ethoxy, propoxy, 3,6-dioxa-heptyla, 3- (trimethylsilyl) -propyl, 4-dimethylaminobutyl, and the like. Unless otherwise specified, heteroalkyl groups can be monovalent or polyvalent, that is, monovalent heteroalkyl or polyvalent heteroalkylene.
    “Aryl is an aromatic group containing 6-18 ring atoms and may contain optional fused rings, which can be saturated, unsaturated, or aromatic. Examples of aryl groups include phenyl, naphthyl, biphenyl, phenanthryl, and anthracyl. Heteroaryl is an aryl containing 1 to 3 heteroatoms such as nitrogen, oxygen, or sulfur, and may contain fused rings. Some examples of heteroaryl groups are pyridyl, furanyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, imidazolyl, indolyl, benzofuranyl, and benzothiazolyl. Unless otherwise specified, aryl and heteroaryl groups may be monovalent or polyvalent, i.e., monovalent aryl or polyvalent arylene.
    “(Hetero) hydrocarbila” is inclusive of alkyl and aryl hydrocarbyl groups, and heteroalkyl and heteroaryl heterohydrocarbyl groups, the latter comprising one or more oxygen heteroatoms in catenary as ether or amino groups. Heterohydrocarbyl may optionally contain one or more functional groups in catenary (chain) form including functional groups ester, amide, urea, urethane, and carbonate. Unless otherwise indicated, non-polymeric (hetero) hydrocarbyl groups typically contain from 1 to 60 carbon atoms. Some examples of such heterohydrocarbons as used herein include, but are not limited to, methoxy, ethoxy, propoxy, 4-diphenylaminobutyl, 2- (2'-phenoxyethoxy) ethyl, 3,6-dioxa-heptyl, 3,6- dioxa-hexyl-6-phenyl, in addition to those described for "alkyl", "heteroalkyl", "aryl", and "heteroaryl" above.
    For use in the present invention, "one", "one", "o", "a", "at least one", "at least one", "one or more" and "one or more are used interchangeably.
    For use in the present invention, recitations of numeric ranges with extremes include all continuous numbers in this range (for example 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc. .).
    Detailed Description
    Dental compositions, dental articles, and methods of use are presently described. The dental composition comprises at least one addition-fragmentation agent. The addition-fragmentation agent comprising at least one ethylenically unsaturated end group and a backbone unit comprising an α, β-unsaturated carbonyl. The addition-fragmentation agent is radically freely cleavable.
    The addition-fragmentation agents are preferably of the following formula:
    5/54
    in which
    R 1 , R 2 and R 3 are each independently Zm-Q-, a (hetero) alkyl group or a (hetero) aryl group with the proviso that at least one of R 1 , R 2 and R 3 is Zm- Q-,
    Q is a linking group that has a valence of m +1;
    Z is an ethylenically unsaturated polymerizable group, m is 1 to 6, preferably 1 to 2;
    each X 1 is independently -O- or -NR 4 -, where R 4 is H or C r C 4 alkyl, and n is 0 or 1.
    Addition-fragmentation agents according to formula I are described in US provisional patent application No. 61/442980, concurrently filed on February 15, 2011; incorporated herein by way of reference.
    In a preferred embodiment, addition-fragmentation materials ("AFM", additionfragmentation materials) can be added in a dental composition comprising at least one ethylenically unsaturated monomer or oligomer. Without sticking to the theory, the inclusion of such addition-fragmentation material is supposed to reduce the stresses induced by polymerization, such as by the mechanism described in provisional patent application US 61/442980. For modalities in which AFMs are multifunctional, comprising at least two ethylenically unsaturated groups (for example Z is â 2 in formula I), the material can function as crosslinking agents, where the crosslinkings are labile.
    The ethylenically unsaturated portion, Z, of the monomer may include, but is not limited to, the following structures, including (meth) acryloyl, vinyl, styrenic and ethynyl, which are more fully described in reference to the preparation of the compounds below.
    0 R 4 R 4 0 R 4 0 N / - r4 w Η θ
    wherein R 4 is H or C1-C4 alkyl.
    In some embodiments, Q is selected from -O-, -S-, -NR 4 -, -SO2-, -PO2-, -CO-, OCO-, -R 6 -, -NR 4 -CO- NR 4 - , NR 4 -CO-O-, NR 4 -CO-NR 4 -CO-OR 6 -, -CO-NR 4 -R 6 -, -R 6 -CO-OR 6 -, -OR 6 -. -SR 6 - -, -NR 4 -R 6 -, -SO2-R 6 -, -PO 2 -R 6 -, -CO-R 6 -, -OCO-R 6 -, -NR 4 -CO-R 6 -, NR 4 -R 6 6/54
    CO-O-, and NR 4 -CO-NR 4 -, where each R 4 is hydrogen, a C 1 to C 4 alkyl group, or aryl group, each R 6 is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms, with the proviso that QZ does not contain peroxidic bonds.
    In some embodiments, Q is an alkylene, as in the formula -C r H 2r -, where r is 1 to 10. In other embodiments, Q is a hydroxyl-substituted alkylene, such as -CH 2 -CH (OH) CH 2 - In some embodiments, Q is an aryloxy-substituted alkylene. In some embodiments, R 5 is alkoxy-substituted alkylene.
    R 1 -X 1 - groups (and optionally R 2 -X 2 - groups) are typically selected from H 2 C = C (CH3) C (O) -O-CK 2 -CH (OH) -CH 2 -O- , H 2 C = C (CH 3 ) C (O) -O-CH 2 -CH (O- (O) C (CH 3 ) = CH 2 ) CH 2 -O-, H 2 C = C (CH 3 ) C (O) -O-CH (CH 2 OPh) -CH 2 -O-, H 2 C = C (CH 3 ) C (O) -O-CH 2 CH 2 -N (H) -C (O ) -OCH (CH 2 OPh) -CH 2 -O-., H 2 C = C (CH 3 ) C (O) -O-CH 2 -CH (O- (O) CN (H) -CH 2 CH 2 -O (O) C (CH 3 ) C = CH 2 ) -CH 2 -O-, H 2 C = C (H) C (O) -O- (CH 2 ) 4 -O-CH 2 -CH (OH) -CH 2 -O-, H 2 C = C (CH3) C (O) O-CH 2 -CH (O- (O) CN (H) -CH 2 CH 2 -O- (O) C (CH 3 ) C = CH 2 ) -CH 2 -O-, CH 3 - (CH 2 ) 7 -CH (O- (O) CN (H) CH 2 CH 2 -O- (O) C (CH 3 ) C = CH 2 ) -CH2-O-, H 2 C = C (H) C (O) -O- (CH 2 ) 4 -O-CH 2 -CH (-O- (O) C (H) = CH 2 ) CH 2 -O- and H 2 C = C (H) C (O) -O-CH 2 -CH (OH) -CH 2 -O-. H 2 C = C (H) C (O) -O- (CH 2 ) 4 -O-CH 2 -CH (-O (O) C (H) = CH 2 ) -CH 2 -O-, and CH 3 - (CH 2 ) 7 -CH (O- (O) CN (H) -CH 2 CH 2 -O- (O) C (CH 3 ) C = CH 2 ) -CH 2 -O-.
    The compounds of formula I can be prepared from (meth) acrylate dimers and trimers by substitution, displacement or condensation reactions. The initial (meth) acrylate dimers and trimers can be prepared by free radical addition of a (meth) acryloyl monomer in the presence of a free radical initiator and a cobalt (II) complex catalyst using the US 4,547,323 process, here incorporated as a reference. Alternatively, (meth) acryloyl dimers and trimers can be prepared using a cobalt chelate complex using the processes of US 4,886,861 (Janowicz) or US 5,324,879 (Hawthorne), incorporated herein by reference. In any process, the reaction mixture can contain a complex mixture of dimers, trimers, higher oligomers and polymers and the desired dimer or trimer can be separated from the mixture by distillation. Such a synthesis is described in detail in the provisional patent application US 61/442980 and in the available examples.
    The concentration of a curable (i.e., polymerizable) dental composition component described herein can be expressed with respect to the polymerizable (i.e., uncharged) resin portion of the dental composition. For preferred embodiments, in which the composition additionally comprises filler, the monomer concentration can also be expressed with respect to the total composition (i. (I.e., charged). When the composition is free of charge, the polymerizable resin portion is equal to the total composition.
    The polymerizable resin portion of the curable (i.e., polymerizable) dental composition described herein comprises at least 0.5% by weight, or 1% by weight, 1.5%
    7/54 by weight, or 2% by weight of addition-fragmentation agent (s). The fragmentation addition agent may comprise a single monomer or a blend of two or more addition-fragmentation agents. The total amount of addition-fragmentation agent (s) in the polymerizable resin portion of the curable (i.e., polymerizable) dental composition is typically not greater than 30% by weight, 25% by weight, 20% by weight, or 15 % by weight. As the concentration of the addition-fragmentation monomer increases, the stress deflection and the Watts contraction typically decrease. However, when the amount of addition-fragmentation agent exceeds an optimal amount, the mechanical properties such as resistance to diametrical tensile strength and / or Barcol hardness, or depth of cure may be insufficient.
    Materials with high polymerization stress under cure generate deformation in the dental structure. A clinical consequence of such tension may be a decrease in the longevity of the restoration. The tension present in the composite passes through the adhesive interface to the dental structure, generating cuspid deflection and cracks in the surrounding dentin and enamel, which can lead to postoperative sensitivity as described in R. R. Cara et al., Particulate Science and Technology 28; 191-206 (2010). Preferred (e.g. loaded) dental compositions (useful for restoration such as fillings and crowns) described here typically exhibit a stress deflection of no more than 2.0, or 1.8, or 1.6, or 1.4, or 1.2 or 1.0 or 0.8 or 0.6 micrometers.
    In other embodiments, the inclusion of the addition-fragmentation agent (s) provides a significant reduction in stress even though the stress deflection is greater than 2.0 micrometers. for example, the inclusion of the addition-fragmentation agent (s) can reduce the strain from about 7 micrometers to about 6, or about 5, or about 4, or about 3 micrometers.
    In some embodiments, the total amount of fragmentation addition agent (s) in the polymerizable resin portion of the curable (i.e., polymerizable) dental composition is not greater than 14% by weight, 13% by weight, or 12% by weight, or 11% by weight, or 10% by weight.
    The curable (i.e., polymerizable) dental composition loaded herein typically comprises at least 0.1% by weight, or 0.15% by weight, or
    0.20% by weight of addition-fragmentation agent (s). The total amount of addition-fragmentation agent (s) in the curable (i.e., polymerizable) dental composition charged to the dental composition is typically not greater than 5% by weight, or 4% by weight, or 3% by weight, or 2 % by weight.
    The curable (e.g. dental) compositions described herein additionally comprise at least one ethylenically unsaturated monomer or oligomer in combination with the addition-fragmentation agent. In some modalities, such as
    8/54 the primers, the ethylenically unsaturated monomer can be monofunctional, having a single ethylenically unsaturated group (for example terminal). In other modalities, such as dental restorations, the ethylenically unsaturated monomer is multifunctional. The phrase "multifunctional ethylenically unsaturated" means that each of the monomers comprises at least two polymerisable ethylenically unsaturated groups (for example via free radicals), such as (meth) acrylate groups.
    In preferred embodiments, such an ethylenically unsaturated group is a group polymerizable via free radicals (e.g. terminal) including (meth) acryl as (meth) acrylamide (H 2 C = CHCON- and H 2 C = CH (CH 3 ) CON-) and (meth) acrylate (CH 2 CHCOO- and CH 2 C (CH 3 ) COO-). Other ethylenically unsaturated polymerizable groups include vinyl (H 2 C = C-) including vinyl ethers (H 2 C = CHOCH-). The terminal (terminal) polymerizable (polymerizable) group (s) is (are) preferably a (meth) acrylate group, particularly for compositions that are hardened by exposure to actinic radiation (e.g. UV). In addition, methacrylate functionality is typically preferred over acrylate functionality in curable dental compositions.
    The ethylenically unsaturated monomer can comprise several ethylenically unsaturated monomers, as known in the art, for use in dental compositions.
    In preferred embodiments, the composition (for example dental) comprises one or more ethylenically unsaturated monomers (for example (meth) acrylate) having a low volume contraction monomer. Preferred (e.g. loaded) dental compositions (useful for restorations such as fillings and crowns) described herein comprise one or more low volume shrinkage monomers such that the composition exhibits less than about 2% Watts contraction. In some modalities, the Watts contraction is not greater than 1.90%, or not greater than 1.80%, or not greater than 1.70%, or not greater than 1.60%. In preferred modalities, the Watts contraction is not greater than 1.50%, or not greater than 1.40%, or not greater than 1.30%, and in some modalities not greater than 1.25% , or not greater than 1.20%, or not greater than 1.15%, or not greater than 1.10%.
    Preferred low volume monomers include isocyanurate monomers, as described in WO2011 / 126647; tricyclodecane monomers, as described in EP application No. 10168240.9, filed on July 2, 2010; polymerizable compounds having at least one cyclic allyl sulfide moiety as described in US2008 / 0194722; methyleneditiepanosilanes as described in US 6,794,520; oxetanesilanes as described in US 6,284,898; and materials containing di-, tri-, and / or tetra- (meth) acryloyl as described in W02008 / 082881; each of which is incorporated by reference.
    In preferred embodiments, most of the polymerizable resin composition (for example uncharged) comprises one or more low shrinkage monomers
    9/54 volume. For example, at least 50%, 60%, 70%, 80%, 90% or more of the polymerizable resin (for example uncharged) comprises low volume shrinkage monomer (s).
    In one embodiment, the dental composition comprises at least one isocyanurate monomer. The isocyanurate monomer generally comprises a trivalent isocyanuric acid ring as an isocyanurate core structure and at least two polymerisable ethylenically unsaturated groups (eg via free radicals) attached to at least two of the nitrogen atoms of the isocyanurate core structure via a linking group (eg divalent). The bonding group is the entire chain of atoms between the nitrogen atom of the isocyanurate core structure and the terminal ethylenically unsaturated group. The ethylenically unsaturated polymerizable groups (for example via free radicals) are generally linked in the core or main chain unit via a linking group (for example divalent).
    The trivalent isocyanurate core structure in general has the formula:
    l
    II o
    The divalent bonding group comprises at least one nitrogen, oxygen or sulfur atom. Such a nitrogen, oxygen or sulfur atom forms a urethane, ester, thioester, ether, or thioether bond. Ether and especially ester bonds can be beneficial over isocyanurate monomers comprising urethane bonds for improved properties such as reduced shrinkage, and / or increased mechanical properties, for example, diametrical tensile strength (DTS). Thus, in some embodiments, the divalent bonding groups of the isocyanurate monomer are free of urethane bonds. In some preferred embodiments, the divalent bonding group comprises an ester bond as an aliphatic or aromatic diester bond.
    The isocyanurate monomer typically has the general structure

    in which Rt is a straight chain, branched or cyclic alkylene, arylene, or alkylene, optionally including a hetero atom (for example oxygen, nitrogen or sulfur); R 2 is hydrogen or methyl; Z is an alkylene, arylene, or alkarylene linking group comprising at least a selected portion of urethane, ester, thioester, ether, or thioether, and combinations of such groups; and at least one of R 3 or R 4 is
    10/54
    Ο
    Fq is typically a straight chain, branched or cyclic alkylene, optionally including a heteroatom, having no more than 12 carbon atoms. In some preferred embodiments, R, has no more than 8, 6 or 4 carbon atoms. In some preferred embodiments, R t comprises at least one hydroxyl moiety.
    In some embodiments, Z comprises an aliphatic or aromatic ester bond as a diester bond.
    In some embodiments, Z additionally comprises one or more ether groups. Therefore, the linking group can comprise a combination of ester or diester groups and one or more ether groups.
    For embodiments, in which the isocyanurate monomer is a di (meth) acrylate monomer, R 3 or R 4 is hydrogen, alkyl, aryl, or alkaryl, optionally including a heteroatom.
    Ri is generally derived from the initial isocyanurate precursor (for example hydroxy-terminated). Various isocyanurate precursor materials are commercially available from TCI America, Portland, OR, USA. The structures of exemplary isocyanurate precursor materials are presented as follows:
    HO,
    OH
    The isocyanurate (meth) acrylate monomers described herein having linking groups comprising an oxygen atom of an ester moiety were generally prepared by reacting hydroxy- or epoxy-terminated isocyanurates with (meth) acrylic carboxylic acids as mono- (2) acid. -methacryloxyethyl) phthalic and mono- (2-methacryloxyethyl) succinic acid.
    Suitable (meth) acrylated carboxylic acids include for example mono- (2-methacryloxyethyl) phthalic acids (s), mono- (2-methacryloxyethyl) succinic acid, and mono- (2-methacryloxyethyl) maleic acid. Alternatively, carboxylic acid may comprise (meth) acrylamide functionality as methacrylamide derivatives of naturally occurring amino acids such as methacrylamidoglycine, methacrylamidoleucine, methacrylamidoalanine etc.
    11/54
    In some embodiments, a single (meth) acrylated carboxylic acid is reacted with a single hydroxyl-terminated isocyanurate (e.g., tris- (2-hydroxylethyl) isocyanurate). When a sufficient molar ratio of carboxylic acid (meth) acrylate is used in such a way that all hydroxyl groups in the ring are reacted, such a synthesis can produce a single reaction product in which each of the groups terminated with free radicals, attached to the atoms nitrogen content of the trivalent isocyanuric acid ring are the same. However, when a single epoxy-terminated isocyanurate is reacted with a single carboxylic acid, the reaction product generally comprises more than one isomer in the reaction product.
    When two different hydroxy- and / or epoxy-terminated isocyanurates and / or two different (for example (meth) acrylated) carboxylic acids are used, a statistical mixture of reaction products is obtained based on the relative quantities of the reagents. For example, when a mixture of an aromatic (meth) acrylated carboxylic acid and an aliphatic (meth) acrylate carboxylic acid is used, some of the divalent radically freely terminated linking groups attached on the nitrogen atom of the trivalent isocyanuric acid ring comprise a group aromatic, while others do not. In addition, when a combination (for example 1 equivalent) of a hydroxyl-terminated carboxylic acid (for example, 2 equivalents) of a monocarboxylic acid (such as octanoic acid) is reacted with a single hydroxyl-terminated isocyanurate (for example tris- (2 -hydroxylethyl) isocyanurate), a mono (meth) acrylate isocyanurate can be prepared as detailed in WO2011 / 126647. Such a mono (meth) acrylate isocyanurate is suitable for use as a reactive diluent.
    Alternatively, isocyanurate (meth) acrylate monomers having bond groups containing ether group can be synthesized. For example, in an illustrative synthesis, phthalic acid anhydride can be reacted with a mono-methacrylated di, tri, tetra or polyethylene glycol in the presence of a catalytic amount of 4- (dimethylamino) pyridine (DMAP) and butylated hydroxytoluene (BHT, butylated hydroxytoluene) at 95 ° C for 3-6 hours to form a mono-methacrylated polyethylene glycol phthalic acid monoester. The methacrylated acid obtained can be reacted, in acetone, with tris- (2hydroxyethyl) isocyanurate using dicyclohexyl-carbodiimide (DCC) at 0-5 ° C then at room temperature. Such a reaction scheme is depicted as follows:
    12/54
    DMAP
    95 ° C, 5 h Ho '

    OH
    DCC
    Acetone
    Recovery
    In another illustrative synthesis, tris (2-hydroxyethyl) isocyanurate can be reacted with ethylene oxide to form polyethylene glycol with a hydroxyl group. OH terminations can be esterified with (meth) acrylic acid to give a product where the linking group is a polyether. Such a reaction scheme is depicted as follows:
    The isocyanurate monomer is preferably a multi (meth) acrylate such as a di (meth) acrylate isocyanurate monomer or a tri (meth) acrylate isocyanurate monomer.
    The di (meth) acrylate monomer has the general structure:

    R 3 in which Ri, R 2 , R3 and Z are as previously described; R 6 is a straight chain, branched, or cyclic alkylene, arylene, or alkylene, optionally including a heteroatom (for example oxygen, nitrogen or sulfur); and Y is bonding group
    Alkylene, arylene, or alkylene, comprising at least a selected portion of urethane, ester, thioester, ether, or thioether, and combinations of such groups.
    Illustrative di (meth) acrylate isocyanurate monomers include:
    In some preferred embodiments, the tri (meth) acrylate monomer has the general structure:

    in which
    14/54
    R 1 ( R 5 , and R 6 are independently a straight chain, branched, or cyclic alkylene, arylene, or alkylene, optionally including a hetero atom (for example oxygen, nitrogen or sulfur); R 2 is hydrogen or methyl; X, Y, and Z are independently an alkylene, arylene, or alkylene group linking at least a selected portion of urethane, ester, thioester, ether, thioether, or combinations of such portions, and R 2 is hydrogen or methyl.
    In some embodiments, R 1 ( R 5 , and R 6 comprise at least one hydroxyl moiety.
    Illustrative tri (meth) acrylate isocyanurate monomers include for example:
    The polymerizable resin portion of the unloadable curable dental composition described herein may comprise at least 10% by weight, 15% by weight, 20% by weight, or
    25% by weight of ethylenically unsaturated multifunctional (multifunctional) isocyanurate monomer (s). The isocyanurate monomer can comprise a single monomer or a blend of two or more isocyanurate monomers. The total amount of isocyanurate monomer (s) in the unloaded polymerizable resin portion of the curable (i.e., polymerizable) dental composition is typically not greater than 90% by weight, 85% by weight, 80% by weight, or 75 % by weight.
    15/54
    In some embodiments, the total amount of isocyanurate monomer (s) in the unloadable curable dental composition is at least 30% by weight, 35% by weight, or 40% by weight and not greater than 70% by weight, 65% by weight, or 60% by weight.
    The curable hardened dental composition described herein typically comprises at least 5% by weight, 6% by weight, 7% by weight, 8% by weight, or 9% by weight of ethylenically unsaturated multifunctional (multifunctional) isocyanurate monomer (s) ( s). The total amount of isocyanurate monomer (s) of the curable (i.e., polymerizable) dental composition loaded is typically not greater than 20% by weight, or 19% by weight, or 18% by weight, or 17% by weight, or 16% by weight, or 15% by weight.
    In another embodiment, the dental composition comprises at least one tricyclodecane monomer. The tricyclodecane monomer can comprise a single monomer or a blend of two or more tricyclodecane monomers. The concentration of ethylenically unsaturated multifunctional tricyclodecane monomer in the polymerizable (i.e., uncharged) resin portion or in the curable (i.e., polymerizable) charged composition may be the same as just described for the ethylenically unsaturated multifunctional isocyanurate monomer.
    In some embodiments, the composition comprises an ethylenically unsaturated multifunctional isocyanurate monomer and ethylenically unsaturated multifunctional tricyclodecane monomer in a weight ratio of about 1.5: 1 to 1: 1.5.
    Tricyclodecane monomers in general have the core structure (ie, the main chain unit (U)):
    In some preferred embodiments, tricyclodecane monomers in general have the core structure (i.e., the main chain unit (U)):
    .— *
    Such tricyclodecane monomers can be prepared, for example, from starting materials such as
    (a + b) = 1 and (c + d) = 1, molecular weight = 312.5
    16/54

    The main chain unit (U) typically comprises one or two spacer unit (s) (S, spacer) connected to the main chain unit (U) via an ether link, at least one spacer unit (S) comprises a CH (Q) -OG chain, in which each group G comprises a (meth) acrylate portion and Q comprises at least one selected group of hydrogen, alkyl, aryl, alkaryl and combinations thereof. In some embodiments, Q is hydrogen, methyl, phenyl, phenoxymethyl, and combinations thereof. G can be connected to the spacer unit (s) via a urethane portion.
    In some embodiments, the spacer unit (s) (S) typically comprise
    Q in which mé1a3; né1a3; eQis hydrogen, methyl, phenyl, phenoxymethyl.
    In other embodiments, the spacer unit (s) typically comprise
    OG in which M = phenyl.
    In some embodiments, the tricyclodecane monomer can be characterized by the structures
    or
    17/54
    with each of these tricyclodecane monomer structures a, b being 0 to 3; c, d = 0 to 3; (a + b) is 1 to 6; (c + d) is 1 to 6; and Q is independently hydrogen, methyl, phenyl or phenoxymethyl.
    Some illustrative species of such multifunctional tricyclodecane monomers
    18/54
    19/54
    The linking groups, isocyanurate monomers and tricyclodecane monomers, are typically of sufficiently low molecular weight such that the monomer is a stable liquid at 25 ° C. However, the linking group (s) is (are) typically higher in molecular weight than the oxygen atom of eg 2,2-bis [4- (2-hydroxy-35 methacryloyloxypropoxy) phenyl] propane (“BisGMA”), a common monomer used in dental compositions, which bonds the (meth) acrylate group to the aromatic ring. The molecular weight of the linking group (s) of the described monomers is typically at least 50 g / mol or 100 g / mol. In some embodiments, the molecular weight of the linking group is at least 150 g / mol. The molecular weight of the linking group is typically not greater than about 500 g / mol. In some embodiments, the molecular weight of the linking group is not greater than 400 g / mol or 300 g / mol.
    In some embodiments, the molecular weight (i.e., calculated) of the low contraction monomer (for example isocyanurate and tricyclodecane) is typically not greater than 2,000 g / mol. In some embodiments, the molecular weight of the monomers is no greater than about 1,500 g / mol or 1,200 g / mol or 1,000 g / mol. The molecular weight of the monomers is typically at least 600 g / mol.
    The increase in molecular weight without forming a solid at 25 ° C can be performed
    20/54 by various synthesis approaches, such as those depicted above. In some embodiments, the linker groups have one or more pending substituents. For example, linker groups can comprise one or more hydroxyl group substituents such as in the case of linker groups comprising alkoxy segments. In other embodiments, the linking groups are branched, and / or comprise at least one cyclic (i.e., aliphatic) moiety, and / or comprise at least one aromatic moiety.
    In some embodiments, a by-product is formed during the synthesis of the monomer which can be a solid at about 25 ° C (ie, +/- 2 ° C). Such a by-product is typically removed from the liquid monomer. Therefore, the liquid monomer is substantially free of such solid fractions. However, it is considered that the liquid monomer may additionally comprise solid reaction by-products (for example non-crystalline) that are soluble in the liquid monomer.
    In some embodiments, the dental composition comprises a polymerizable compound having at least one cyclic allyl sulfide moiety with at least one (meth) acryloyl moiety.
    Such a polymerizable compound is here called a hybrid monomer or a hybrid compound. The cyclic allyl sulfide moiety typically comprises at least one 7 or 8 membered ring that has two heteroatoms in the ring, one of which is sulfur. Most typically both heteroatoms are sulfur, which can optionally be present as part of an SO, SO 2 , or SS moiety. In other embodiments, the ring may comprise a sulfur atom plus a second different heteroatom in the ring, such as oxygen or nitrogen. In addition, the cyclic allylic moiety may comprise multi-ring structures, i.e., it may have two or more cyclic allyl sulfide moieties. The (meth) acryloyl portion is preferably a (meth) acryloyloxyl (i.e., a (meth) acrylate portion) or a (meth) acryloylamino (i.e., a (meth) acrylamide portion).
    In one embodiment, the low contraction monomer includes those represented by the formulas:
    or
    21/54
    Formula 1b
    In the above formulas, each X can be independently selected from S, O, N, C (for example CH 2 or CRR, where each R is independently an H or an organic group), SO group, SO 2 , N-alkyl, N -acyl, NH, N-aryl, carboxyl or carbonyl, provided that at least one X is S or a group comprising S. Preferably, each X is S.
    Y is either alkylene (e.g. methylene, ethylene, etc.) optionally including a heteroatom, carbonyl, or acyl; or is absent, thus indicating the size of the ring, typically 7 to 10 membered rings, however larger rings are also considered. Preferably, the ring is either a 7-membered or an 8-membered ring with Y therefore being absent or being methylene, respectively. In some embodiments, Y is either absent or is a C 1 to C 3 alkylene, optionally including a heteroatom, carbonyl, acyl, or combinations thereof.
    Z is O, NH, N-alkyl (branched or straight chain), or N-aryl (phenyl or substituted phenyl).
    The R 'group represents a linker group selected from alkylene groups (typically having more than one carbon atom, ie excluding methylene), alkylene optionally including a hetero atom (for example O, N, S, SS, SO , SO2), arylene, cycloaliphatic, carbonyl, siloxane, starch (-CO-NH-), acyl (-CO-O-), urethane (-0CO-NH-), and urea (-NH-CO-NH-) , and their combinations. In certain embodiments, R 'comprises an alkylene group, typically a methylene group or longer, which can be either straight or branched, and which can be either unsubstituted or substituted with aryl, cycloalkyl, halogen, nitrile, alkoxy group , alkylamino, dialkylamino, alkylthio, carbonyl, acyl, acyloxy, starch, urethane group, urea group, a cyclic allyl sulfide moiety, or combinations thereof.
    R ”is selected from H, and CH 3 , and“ a ”and“ b ”are independently 1 to 3.
    Optionally the cyclic allyl sulfide moiety may be additionally substituted on the ring with one or more groups selected from straight or branched chain alkyl, aryl, cycloalkyl, halogen, nitrile, alkoxy, alkylamino, dialkylamino, alkylthio, carbonyl, acyl, acyloxyl, starch, urethane group, and urea group. preferably the selected substituents do not interfere with the hardening reaction. Preferred are cyclic allyl sulfide structures that comprise unsubstituted methylene members.
    A typical low shrinkage monomer can comprise a sulfide moiety
    22/54 8-membered cyclic allyl with two sulfur atoms in the ring and with the linker group linked directly at position 3 of the ring with an acyl group (ie, OC-ring (O) -). Typically the average molecular weight (MW) of the hybrid monomer ranges from about 400 to about 900 and in some embodiments it is at least 250, more typically at least 500, and much more typically at least 800.
    Representative polymerizable compounds having at least one cyclic allyl sulfide moiety with at least one (meth) acryloyl moiety include the following
    The inclusion of a polymerizable compound having at least one cyclic allyl sulfide moiety may result in a synergistic combination of low volume contraction in combination with high resistance to diametrical traction.
    In another embodiment, the dental composition comprises a low shrinkage monomer that includes at least one of the materials containing di, tri, and / or tetra (meth) acryloyl having the general formula:
    THE,
    ( γ γ -ο>'
    Ο
    R 1 where: each X independently represents an oxygen atom (O) or a nitrogen atom (N); Y and A each independently represent an organic group, and R 1 represents -C (O) C (CH3) = CH2, and / or (ii) q - 0 and R 2 represents C (O) C (CH3) = CH 2 ; m = 1a5; n = 0a5; p and q are independently 0 or 1; and R 1 and R 2
    23/54 independently represent, each, H, -C (O) CH = CH 2 , or -C (O) C (CH 3 ) = CH 2 . In some embodiments, Y does not represent -NHCH 2 CH 2 - when p = 0. Although, this material is a derivative of bisphenol A, when other low volume contraction monomers are used, such as isocyanurate and / or tricyclodecane monomers, the dental composition is free of (meth) aerilate monomers derived from bisphenol A.
    Low-shrink multifunctional monomers (for example isocyanurate and tricyclodecane) are liquid (for example high) viscous at about 25 ° C, still able to flow. The viscosity as can be measured with a Haake RotoVisco RV1 device, as described in EP application No. 10168240.9, filed on July 2, 2010; it is typically at least 300, or 400, or 500 Pa.s and not greater than 10,000 Pa.s. In some embodiments, the viscosity is not greater than 5,000 or 2,500 Pa.s.
    The ethylenically unsaturated monomers of the dental composition are typically liquid stable at about 25 ° C meaning that the monomer does not substantially polymerize, crystallize, or otherwise solidify when stored at room temperature (about 25 ° C) for a typical shelf life at least 30, 60, or 90 days. The viscosity of monomers typically does not change (for example increase) by more than 10% of the initial viscosity.
    Particularly for dental restoration compositions, ethylenically unsaturated monomers in general have a peto refractive index minus 1.50. In some embodiments, the refractive index is at least 1.51, 1.52, 1.53, or greater. The inclusion of sulfur atoms and / or the presence of one or more aromatic groups can increase the refractive index (in relation to the monomer of the same molecular weight without such substituents).
    In some embodiments, the polymerizable (uncharged) resin may comprise only one or more low shrinkage monomers in combination with the addition-fragmentation agent (s). In other embodiments, the polymerizable (uncharged) resin comprises a small concentration of other monomer (s). "Other" is intended to mean an ethylenically unsaturated monomer such as a (meth) acrylate monomer that is not a low volume contraction monomer.
    The concentration of such other monomer (s) is typically not greater than 20% by weight, 19% by weight, 18% by weight, 17% by weight, 16% by weight, or 15% by weight. weight of the portion of polymerizable resin (unloaded). The concentration of such other monomers is typically not greater than 5% by weight, 4% by weight, 3% by weight, or 2% by weight of the charged polymerizable dental composition.
    In some embodiments, the dental composition comprises a reactive (i.e., polymerizable) diluent of low viscosity. Reactive diluents typically have a viscosity as measured with a Haake RotoVisco RV1 device, as described in EP application No. 10168240.9, filed on July 2, 2010, of no greater
    24/54 than 300 Pa.s and preferably not greater than 100 Pa.s, or 50 Pa.s, or 10 Pa.s. In some embodiments, the reactive diluent has a viscosity of no more than 1 or 0.5 Pa.s. Reactive diluents are typically relatively low in molecular weight, having a molecular weight of less than 600 g / mol, or 550 g / mol, or 500 g / mol. Reactive diluents typically comprise one or two ethylenically unsaturated groups as in the case of mono (meth) acrylate or di (meth) acrylate monomers.
    In some embodiments, the reactive diluent is an isocyanurate or tricyclodecane monomer. The tricyclodecane reactive diluent can generally have the same structure as previously described. In preferred embodiments, the tricyclodecane reactive diluent comprises one or more spacer unit (s) (S) being connected to the main chain unit (U) via an ether bond; as described in EP application No. 10168240.9, filed on July 2, 2010; incorporated herein by reference. An illustrative reactive tricyclodecane thinner has the general structure:
    o (a + b) = 1 and (c + d) = 1, molecular weight = 448.6; n D 20 - 1,499; η = 0.1 Pa.s.
    Although the inclusion of an addition-fragmentation agent in a low volume contraction composition typically provides the lowest stress and / or the lowest contraction, the addition-fragmentation agents described herein can also reduce the tension and contraction of the composition. dentistry comprising conventional hardenable (meth) acrylate monomers, such as ethoxylated bisphenol A dimethacrylate (BisEMA6), 2-hydroxyethyl methacrylate (HEMA), bisphenol-A-diglycidyl dimethacrylate (bisGMA), urethane dimethyl acrylate (UMA) dimethyl acrylate (UDMA) (TEGDMA), glycerol dimethacrylate (GDMA), ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate (NPGDMA), and polyethylene glycol dimethacrylate (PEGDMMA).
    The curable component of the curable dental composition can include a wide variety of other ethylenically unsaturated compounds (with or without acid functionality), epoxy-functional (meth) acrylate resins, vinyl ethers, and the like.
    Dental compositions (for example photopolymerizable) can include monomers polymerizable via free radicals, oligomers, and polymers having one or more ethylenically unsaturated groups. Suitable compounds contain at least one ethylenically unsaturated bond and can be subjected to polymerization by addition. Examples of useful ethylenically unsaturated compounds include acrylic acid esters, methacrylic acid esters, hydroxy-functional acrylic acid esters, hydroxy-functional methacrylic acid esters, and combinations thereof. These polymerizable compounds via free radicals include
    25/54 mono, di or poly (meth) acrylates (i.e., acrylates and methacrylates) such as (meth) methyl acrylate, (meth) ethyl acrylate, (meth) isopropyl acrylate, (meth) n-hexyl acrylate , stearyl (meth) acrylate, allyl (meth) acrylate, glycerol tri (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, di (meth) triethylene glycol acrylate, di (meth) acrylate ) 1,3propanediol acrylate, trimethylolpropane tri (meth) acrylate, 1,2,4-butanotriol tri (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, pentaerythritol tetra (meth) acrylate , sorbitol hex (meth) acrylate, tetrahydro-furfuryl (meth) acrylate, bis [1- (2-acryloxy)] - p-ethoxy-phenyldimethylmethane, bis [1 (3-acryloxy-2-hydroxy)] -p-propoxyphenyldimethiomethane, ethoxylated bisphenol A di (meth) acrylate and trishydroxyethylisocyanurate tri (meth) acrylate; (meth) acrylamides (i.e., acrylamides and methacrylamides) such as methacrylamide, methylene-bis-methacrylamide and diacetone-methacrylamide; (met) urethane acrylates; Bis- (meth) acrylates of polyethylene glycols (preferably molecular weight 200-500); and vinyl compounds such as styrene, diaryl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate. Other suitable free radical polymerizable compounds include siloxane-functional (meth) acrylates. Mixtures of two or more free radical polymerizable compounds can be used if desired.
    The curable dental composition can also contain a monomer having hydroxyl groups and ethylenically unsaturated groups in a single molecule. Examples of such materials include hydroxyalkyl (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; glycerol mono- or di- (meth) acrylate; trimethylolpropane mono- or di- (meth) acrylate; pentaerythritol mono-, di- and tri- (meth) acrylate; sorbitol mono-, di-, tri-, tetra- or penta- (meth) acrylate; and 2,2-bis [4- (2-hydroxy-3-ethacryloxypropoxy) phenyl] propane (bis GMA). Suitable ethylenically unsaturated compounds are available from a wide variety of commercial sources, such as Sigma-Aldrich, St. Louis, USA.
    The dental compositions described herein can include one or more curable components in the form of ethylenically unsaturated compounds with acid functionality. Such components contain acidic groups and ethylenically unsaturated groups in a single molecule. When present, the polymerizable component optionally comprises an ethylenically unsaturated compound with acid functionality. Preferably, the acid functionality includes an oxyacid (i.e., an oxygen-containing acid) of carbon, sulfur, phosphorus, or boron.
    For use in the present invention, ethylenically unsaturated compounds with acid functionality are intended to include monomers, oligomers, and polymers having ethylenic unsaturation and acid and / or acid precursor functionality. The precursor functionalities of acid include, for example, anhydrides, acid halides, and pyrophosphates. Acid functionality may include carboxylic acid functionality, phosphoric acid functionality, phosphonic acid functionality, sulfonic acid functionality, or combinations thereof.
    Ethylenically unsaturated compounds with acid functionality include, for example,
    26/54 example, α, β-unsaturated acid compounds such as glycerol-phosphate-mono (meth) acrylates, glycerol-phosphate-di (meth) acrylates (GDMA-P), hydroxyethyl (meth) acrylate (eg HEMA) phosphates, bis ((met) acryloxypropyl) phosphate, ((met) acryloxypropyl phosphate), bis ((met) acryloxypropyl) phosphate, bis ((met) acryloxy) propyloxy phosphate, (met) acryloxyhexyl phosphate, bis phosphate ((meth) acryloxyhexyl), (meth) acryloxycyl phosphate, bis ((meth) acryloxyethyl phosphate, (meth) acryloxydecyl phosphate, bis ((meth) acryloxydecyl phosphate, caprolactone-methacrylate-phosphate, di - or citric acid tri-methacrylates, oligo (maleic acid) poly (met) acrylate, polyphacid maleic) poly (met) acrylate, poly ((meth) acrylic) poly (meth) acrylate, polycarboxyl-poly (phosphonic acid) poly (meth) acrylate, poly (chlorophosphonic acid) poly (meth) acrylate, poly (meth) acrylated polysulfonate, boric polifacid) poly (meth) acrylate, and the like, can be used as components. Also monomers, oligomers, and polymers of unsaturated carbonic acids such as (meth) acrylic acids, aromatic (meth) acrylated acids (e.g. methacrylated trimellitic acids), and anhydrides thereof.
    Dental compositions can include an ethylenically unsaturated compound with acid functionality that has at least one P-OH moiety. These compositions are self-adhesive and non-aqueous. For example, such compositions may include: a first compound including at least one (meth) acryloxyl group and at least one -Ο-Ρ (Ο) (ΟΗ) χ group, where x = 1 or 2, and the hair being at least one -OP (O) (OH) X group and at least one (meth) acryloxy group are linked by a C1-C4 hydrocarbon group; a second compound including at least one (meth) acryloxyl group and at least one -OP (O) (OH) X group , where x = 1 or 2, and the at least one -OP (O) (OH) group ) X and the at least one (meth) acryloxy group are linked by a C5-C12 hydrocarbon group; an ethylenically unsaturated compound without acid functionality; an initiator system; and a charge.
    Curable dental compositions can include at least 1% by weight, at least 3% by weight, or at least 5% by weight of ethylenically unsaturated compounds with acid functionality, based on the total weight of the uncharged composition. The compositions can include a maximum of 80% by weight; maximum 70% by weight; or at most 60% by weight of ethylenically unsaturated compounds with acid functionality. In some embodiments, a curable dental composition comprising at least 10% by weight to about 30% by weight of ethylenically unsaturated compounds with acid functionality, such as a mixture of HEMA and GDMA-P, is described.
    Curable dental compositions can include resin-modified glass ionomer cements such as those described in US Patent No. 5,130,347 (Mitra) 5,154,762 (Mitra) 5,962,550 (Akahane). Such compositions can be powder-liquid, paste-liquid or paste-paste systems. Alternatively, copolymer formulations such as those described in US Patent No. 6,126,922 (Rozzi) are included in the scope of the invention.
    27/54
    A initiator is typically added to the mixture of polymerizable ingredients. The initiator is sufficiently miscible with the resin system to allow prompt dissolution in (and prevent separation of) the polymerizable composition. Typically, the initiator is present in the composition in effective amounts, such as from about 0.1 weight percent to 5.0 weight percent, based on the total weight of the composition.
    The addition-fragmentation agent is in general radically freely cleavable. Although light curing is a mechanism for the generation of free radicals, other healing mechanisms also generate free radicals. Thus, the fragmentation addition agent does not require irradiation with actinic radiation (for example photocure) in order to provide a reduction in tension during curing.
    In some embodiments, the monomer mixture is light cured and the composition contains a photoinitiator (that is, a photoinitiator system) which under irradiation with actinic radiation initiates the polymerization (or hardening) of the composition. Such photopolymerizable compositions can be polymerized via free radicals. The photoinitiator typically has a functional wavelength range from about 250 nm to about 800 nm. Suitable photoinitiators (i.e., photoinitiator systems that include one or more compounds) for the polymerization of photopolymerizable compositions via free radicals include binary and tertiary systems. Typical tertiary photoinitiators include an iodonium salt, a photosensitizer, and an electron donor compound as described in US Patent No. 5,545,676 (Palazzotto et al.). Iodonium salts include diaryliodonium salts, for example, diphenyliodonium chloride, diphenyliodonium hexafluorophosphate and diphenyliodonium tetrafluoroborate. Some preferred photosensitizers can include monocetones and diketones (e.g. alpha-diketones) that absorb some light within a range of about 300 nm to about 800 nm (preferably about 400 nm to about 500 nm) as camphorquinone, benzyl, furyl, 3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone and other cyclic alpha-diketones. Among these, camphorquinone is typically preferred. Preferred electron donor compounds include substituted amines, for example, ethyl 4- (N, N-dimethylamino) benzoate.
    Other photoinitiators suitable for the polymerization of photopolymerizable compositions via free radicals include the class of phosphine oxides which typically have a functional wavelength range from about 380 nm to about 1,200 nm. Preferred phosphine oxide free radical initiators with a functional wavelength range from about 380 nm to about 450 nm are acylphosphine and bisacylphosphine oxides.
    Commercially available phosphine oxide photoinitiators capable of initiation via free radicals when irradiated in wavelength ranges greater than 380 nm to 450 nm include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819, Ciba Specialty Chemicals , Tarrytown, NY, USA), bis (2,6-dimethoxybenzoyl) 28/54 (2,4,4-trimethylpentyl) phosphine oxide (CGI 403, Ciba Specialty Chemicals), a 25:75 mixture, by weight, of bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine and 2-hydroxy-2-methyl-1-phenylpropane-1-one oxide (IRGACURE 1700, Ciba Specialty Chemicals), a 1: 1 mixture, by weight, bis (2,4,6-trimethylbenzoyl) phenylphosphine and 2-hydroxy-2-methyl-1-phenylpropane-1one oxide (DAROCUR 4265, Ciba NC Specialty Chemicals), and ethyl 2,4,6-tnmethylbenzylphenylphosphinate (LUCIRIN LR8893X, BASF Corp., Charlotte, NC, USA).
    Tertiary amine-based reducing agents can be used in combination with an acylphosphine oxide. Illustrative tertiary amines include 4- (N, N-dimethylamino) ethyl benzoate and Ν, Ν-dimethylaminoethyl methacrylate. When present, the amine-based reducing agent is present in the light-curing composition in an amount of about 0.1 percent, to about 5.0 percent, by weight, based on the total weight of the composition. In some embodiments, the curable dental composition can be irradiated with ultraviolet (UV) rays. For this modality, suitable photoinitiators include those available under the trade names IRGACURE and DAROCUR from Ciba Specialty Chemical Corp., Tarrytown, NY, USA and include 1-hydroxy-cyclohexylphenyl ketone (IRGACURE 184), 2,2-dimethoxy- 1,2-diphenylethan-1-one (IRGACURE 651), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (IRGACURE 819), 1- [4- {2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1propane-1-one (IRGACURE 2959), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone (IRGACURE 369), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan -1-one (IRGACURE 907) and 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173).
    Photopolymerizable compositions are typically prepared by mixing the various components of the compositions. For modalities in which the photopolymerizable compositions are not cured in the presence of air, the photoinitiator is combined under "safe light" conditions (ie conditions that do not cause premature curing of the composition). Suitable inert solvents can be used, if desired, when preparing the mixture. Examples of suitable solvents include acetone and dichloromethane.
    Hardening is affected by exposure of the composition to a radiation source, preferably a visible light source. It is convenient to use light sources that emit light of actinic radiation between 250 nm and 800 nm (particularly blue light with a wavelength of 380 to 520 nm) such as quartz halogen lamps, tungsten-halogen lamps, mercury arcs, carbon arcs, low, medium and high pressure mercury lamps, plasma arcs, light-emitting diodes and lasers. In general, useful light sources have intensities in the range of 0.200 to 1,000 W / cm 2 . A variety of conventional lights for curing such compositions can be used.
    The exhibition can be carried out in several ways. For example, the polymerizable composition can be continuously exposed to radiation throughout the curing process (for example about 2 seconds to about 60 seconds). It is also
    29/54 it is possible to expose the composition to a single dose of radiation and then remove the radiation source, thereby allowing polymerization to occur. In some cases, the materials may be subjected to light sources that change from low to high intensity. Where double exposures are used, the intensity of each dosage can be the same or different. Similarly, the total energy for each exposure can be equal or different.
    Dental compositions comprising ethylenically unsaturated multifunctional monomers can be chemically curable, i.e., the compositions contain a chemical initiator (i.e., initiator system) that can polymerize, cure, or otherwise harden the composition without reliance on irradiation with actinic radiation. This chemically curable composition (for example polymerizable or curable) is often called a “self-curing” composition and can include redox curing systems, thermal curing systems and combinations thereof. In addition, the polymerizable composition may comprise a combination of different initiators, at least one of which is suitable for initiating polymerization via free radicals.
    The chemically curable compositions can include redox curing systems that include a polymerizable component (for example an ethylenically unsaturated polymerizable component) and redox agents that include an oxidizing agent and a reducing agent.
    The oxidizing and reducing agents react with or otherwise cooperate with each other to produce free radicals capable of initiating the polymerization of the resin system (for example the ethylenically unsaturated component). This type of cure is a reaction in the dark, that is, it does not depend on the presence of light and can occur in the absence of light. The oxidizing and reducing agents are preferably sufficiently stable during storage and free from undesirable coioration to allow their storage and use under typical conditions.
    Useful reducing agents include ascorbic acid, ascorbic acid derivatives and metal complexed ascorbic acid compounds as described in US Patent No. 5,501,727 (Wang et al.); amines, especially tertiary amines, such as 4-tert-butyldimethylaniiine; aromatic sulfinic salts, such as p-toluenesulfinic salts and benzenesulfinic salts; thioureas, such as 1-ethyl-2-thiourea, tetraethylthiourea, tetramethylthiourea, 1,1dibutylthiourea and 1,3-dibutylthiourea; and their mixtures. Other secondary reducing agents can include cobalt (II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine (depending on the choice of oxidizing agent), salts of a dithionite or sulfite anion, and mixtures thereof. Preferably, the reducing agent is an amine.
    Suitable oxidizing agents will also be familiar to those skilled in the art, and include but are not limited to persulfuric acid and its salts, such as sodium, potassium, ammonium, cesium, and alkylammonium salts. Additional oxidizing agents include
    30/54 peroxides such as benzoyl peroxide, hydroperoxides such as cumyl hydroperoxide, t-butyl hydroperoxide, and amyl hydroperoxide, as well as transition metal salts such as cobalt (III) chloride and ferric chloride, cerium (IV) sulfate , perboric acid and its salts, permanganic acid and its salts, perfosphoric acid and its salts, and mixtures thereof.
    It may be desirable to use more than one oxidizing agent or more than one reducing agent. Small amounts of transition metal compounds can also be added to accelerate the redox cure rate. Oxidizing or reducing agents can be microencapsulated as described in US Patent No. 5,154,762 (Mitra et al.). This, in general, will increase the stability during storage of the polymerizable composition and, if necessary, allow the joint packaging of reducing and oxidizing agents. For example, through the proper selection of an encapsulating agent, oxidizing and reducing agents can be combined with an acidic functional component and optional charge and kept in a stable state for storage.
    The curable dental compositions can also be cured thermally or by a thermally activated free radical initiator. Typical thermal initiators include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile, and also dicumyl peroxide, which is preferred for blocks of raw material for machining.
    In preferred embodiments, such as when the dental composition is used as a dental restorative (for example crown or dental filling) or an orthodontic cement, the dental composition typically comprises appreciable amounts of filler (for example nanoparticle). Compositions of this type preferably include at least 40% by weight, more preferably at least 45% by weight, and most preferably at least 50% by weight of filler material, based on total weight of the composition. In some embodiments, the total amount of filler material is at most 90% by weight, preferably at most 80% by weight, and more preferably at most 75% by weight of filler material.
    Dental composite materials (e.g. filled) typically exhibit a diametrical tensile strength (DTS) of at least about 70, 75, or 80 MPa and / or a Barcol hardness of at least about 60, or 65, or 70 , or 75. The depth of cure varies from about 4 to about 5 and comparable with commercially available (e.g. loaded) dental compositions suitable for restorations.
    In some embodiments, the compressive strength is at least 300, 325, 350 or 375 MPa.
    In some embodiments, as compositions additionally comprising at least one ethylenically unsaturated monomer with acid functionality, the adhesion to the enamel and / or dentin is at least 5, 6, 7, 8, 9, or 10 MPa.
    Dental compositions suitable for use as dental adhesives can also
    Optionally include filler in an amount of at least 1% by weight, 2% by weight, 3% by weight, 4% by weight, or 5% by weight based on the total weight of the composition. For modalities of this type, the total concentration of filler material is a maximum of 40% by weight, preferably a maximum of 20% by weight and, more preferably, a maximum of 15% by weight, of loading material, based on the total weight of the composition.
    The filler materials can be selected from one or more of a wide variety of materials suitable for incorporation into compositions used for dental applications, as filler materials currently used in restorative and similar dental compositions.
    The charge can be an inorganic material. It can also be a cross-linked organic material that is insoluble in the polymerizable resin and is optionally filled with inorganic filler material. The loading material is, in general, non-toxic and suitable for use in the mouth. The loading material can be radiopaque, radiolucent or non-radiopaque. Loading materials, when used in dental applications, are typically ceramic in nature.
    Inorganic non-reactive acid particles include quartz (i.e., silica), submicrometric silica, zirconia, submicrometric zirconia, and non-vitreous microparticles of the type described in US Patent No. 4,503,169 (Randklev).
    The charge can also be an acid reactive charge. Reactive acidic charges include metal oxides, glass, and metal salts. Typical metal oxides include barium oxide, calcium oxide, magnesium oxide, and zinc oxide. Typical glasses include borate glasses, phosphate glasses and fluoroaluminosilicate (“FAS”) glasses. FAS glass typically contains cations that are sufficiently elucible for a hardened dental composition to form when the glass is mixed with the components of the curable composition. The glass also typically contains fluoride ions sufficiently readable for the cured composition to have cariostatic properties. Glass can be produced from a molten material containing fluoride, alumina, and other glass-forming ingredients using techniques familiar to those skilled in the FAS glass making technique. FAS glasses are typically in the form of particles that are sufficiently finely divided so that they can be conveniently mixed with the other cement components and will work well when the resulting mixture is used in the mouth.
    In general, the average particle size (typically, diameter) of the FAS glass is not more than 12 micrometers, typically not more than 10 micrometers and, more typically, not more than 5 micrometers, as measured with use, for example, of a particle size analyzer by sedimentation. Suitable FAS glasses will be familiar to those skilled in the art, and are available from a wide variety of commercial sources, and many are found in glass ionomer cements currently available as those commercially available under the trade names VITREMER, VITREBOND,
    32/54
    RELY X LUTING CEMENT, RELY X LUTING PLUS CEMENT, PHOTAC-FIL GUICK, KETACMOLAR and KETAC-FIL PLUS (3M ESPE Dental Products, St. Paul, MN, USA), FUJI II LC and FUJI IX (GC Dental Industrial Corp., Tokyo, Japan) and CHEMFIL Superior (Dentspiy International, York, PA, USA). Charge mixes can be used if desired.
    Other suitable fillers are described in US patents No. 6,387,981 (Zhang et al.) And 6,572,693 (Wu et al.) And also in international PCT publications No. WO 01/30305 (Zhang et al.), US patent No. 6,730,156 (Windisch et al.), WO 01/30307 (Zhang et al.), and WO 03/063804 (Wu et al.). The charge components described in these references include nanometer-sized silica particles, nanometer-sized metal oxide particles, and combinations thereof. Nanocharges are also described in US patents No. 7,090,721 (Craig et al.), 7,090,722 (Budd et al.) And 7,156,911; and US patent No. 7,649,029 (Kolb et al.).
    Examples of suitable organic filler particles include polycarbonates, polyepoxides, sprayed poly (meth) acrylates with or without filler material, and the like. The dental filler particles commonly used are quartz, submicrometric silica and non-vitreous microparticles of the type described in US Patent No. 4,503,169 (Randklev).
    Mixtures of these filler materials can also be used, as well as filler combinations made from organic and inorganic materials.
    Loading materials can be particulate or fibrous in nature. Particulate filler materials can, in general, be defined as those that have a length to width ratio (or aspect ratio) of 20: 1 or less and, more commonly, 10: 1 or less. Fibrous materials can be defined as those with aspect ratios greater than 20: 1 or, more commonly, greater than 100: 1. The shape of the particles can vary from spherical to ellipsoidal or flatter like flakes or discs. Macroscopic properties can be highly dependent on the shape of the charge particles, in particular the uniformity of the shape.
    Micrometric size particles are very effective in improving wear properties after curing. In contrast, nanoscopic loading materials are commonly used as viscosity and thixotropy modifiers. Due to their small size, their large surface area and their bond associated with hydrogen, it is known that these materials come together in aggregate networks.
    In some embodiments, the dental composition preferably comprises a nanoscopic particulate charge (i.e., a charge comprising nanoparticles) that has an average primary particle size of less than about 0.100 micrometer (i.e., pm) and, most preferably , less than 0.075 pm. For use in the present invention, the term "primary particle size" refers to the size of a single, unassociated particle. The average primary particle size can be determined by cutting a fine sample of the hardened tooth composition and measuring the particle diameter of about 5033/54
    100 particles using a transmission electron micrograph at an enlargement of 300,000 and averaging. The charge can have a unimodal or polimodal (for example bimodal) particle size distribution. The nanoscopic particulate material typically has an average primary particle size of at least about 2 nanometers (nm) and, preferably, at least about 7 nm. Preferably, the nanoscopic particulate material has an average primary particle size of no more than about 50 nm and, more preferably, no more than about 20 nm in size. The average surface area of a cargo material of this type is preferably at least about 20 square meters per gram (m 2 / g), more preferably at least about 50 m 2 / g, most preferably, at least about 100 m 2 / g.
    In some preferred embodiments, the dental composition comprises silica nanoparticles. Suitable nanometric silicas are commercially available from Nalco Chemical Co. (Naperville, IL, USA) under the product designation NALCO COLLOIDAL SILICAS. For example, the preferred silica particles can be obtained using NALCO 1040, 1042, 1050, 1060, 2327 and 2329 products.
    The silica particles are preferably produced from an aqueous colloidal dispersion of silica (i.e., a sun or an aqua). Colloidal silica is typically found in the concentration of about 1 to 50 weight percent of the silica sol. Colloidal silica sols that can be used are commercially available having different colloidal sizes, see Surface & Colloid Science, Vol. 6, ed. Matijevic, E., Wiley Interscience, 1973. Preferred silica sols for use in preparing the inventive filler materials are those distributed as a dispersion of amorphous silica in an aqueous medium (such as Nalco's colloidal silicas distributed by Nalco Chemical Company) and those that have a low sodium concentration and can be acidified by admixing it with a suitable acid (eg colloidal silica Ludox, manufactured by EI Dupont de Nemours & Co. or Nalco 2326, available from Nalco Chemical Co.).
    Preferably, the silica particles in the sol have an average particle diameter of about 5-100 nm; more preferably, 10-50 nm; and, most preferably, 1240 nm. A particularly preferred silica sol is NALCO 1041.
    In some embodiments, the dental composition comprises zirconia nanoparticles.
    Suitable nanometric zirconia nanoparticles can be prepared using hydrothermal technology, as described in US patent No. 7,241,437 (Davidson et al.).
    In some embodiments, nanoparticles with a lower refractive index (eg silica) are used in combination with nanoparticles with a higher refractive index (eg zirconia) so that the index is compatible (refractive index within 0.02) with the refractive index of the polymerizable resin.
    34/54
    In some embodiments, the nanoparticles are in the form of nano-clusters, that is, a group of two or more particles associated by relatively weak intermolecular forces that cause the particles to group together, even when dispersed in a hardenable resin.
    Preferred nanoaggregations may comprise a substantially amorphous grouping of unweighted particles (for example silica) and heavy amorphous metal oxide particles (i.e., which have an atomic number greater than 28) such as zirconia. The particles of the nanoaggregation preferably have an average diameter of less than about 100 nm. Suitable nano-cluster loads are described in US patent No. 6,730,156 (Windisch et al.); incorporated herein by way of reference.
    In some preferred embodiments, the dental composition comprises silica nanoparticles and / or nano-clusters subjected to surface treatment with an organo-metallic copulating agent to optimize the bond between the filler material and the resin. The organo-metallic copulating agent can be functionalized with reactive curing groups, such as acrylates, methacrylates, vinyl groups and the like.
    Suitable copolymerizable organo-metallic compounds can have the general formulas: CH 2 = C (CH 3 ) m Si (OR) n or CH 2 = C (CH 3 ) mC = OOASi (OR) n ; where m is 0 or 1, R is an alkyl group having 1 to 4 carbon atoms, A is a divalent organic bonding group, and n is 1 to 3. Preferred copulating agents include gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane and the like.
    In some embodiments, a combination of surface modifying agents can be useful, with at least one of the agents having a functional group copolymerizable with a curable resin. Other surface modifying agents that generally do not react with curable resins can be included to improve rheological properties or dispersibility. Examples of silanes of this type include, for example, arylpolyethers, silanes functionalized with alkyl, hydroxyalkyl, hydroxylaryl or aminoalkyl.
    The surface modification can be done either subsequent to mixing with the monomers or after mixing. It is typically preferable to combine the organosilane surface treatment compounds with the nanoparticles prior to their incorporation into the resin. The amount of surface modifier required depends on several factors such as particle size, particle type, molecular weight of the modifier and type of the modifier. In general, it is preferable that approximately a single layer of modifier is attached to the surface of the particle.
    Surface-modified colloidal nanoparticles can be substantial and fully condensed. Fully condensed nanoparticles (with the exception of silica) typically have a degree of crystallinity (measured as isolated metal oxide particles) greater than 55%, preferably greater than 60%, and more preferably greater than
    35/54
    70%. For example, the degree of crystallinity can vary up to about 86% or more. The degree of crystallinity can be determined by X-ray diffraction techniques. Crystalline condensed nanoparticles (eg zirconia) have a high refractive index, while amorphous nanoparticles typically have a lower refractive index.
    In some embodiments, dental compositions may have an initial color notably different from that of cured dental structures. Color can be added to the composition through the use of a photoclare or thermochromic dye. For use in the present invention, "photoclare" refers to the loss of color upon exposure to actinic radiation. The composition can include at least 0.001%, by weight, of photocellable or thermochromic dye and, typically, at least 0.002%, by weight, of photocellable or thermochromic dye, based on the total weight of the composition. The composition typically includes a maximum of 1% by weight of a photoclare or thermochromic dye and, more typically, a maximum of 0.1% by weight of a photoclare or thermochromic dye, based on the total weight of the composition, A The amount of photoclare or thermochromic dye can vary depending on its extinction coefficient, the ability of the human eye to discern its initial color, and the desired color changes. Suitable thermochromic dyes are shown, for example, in US Patent No. 6,670,436 (Burgath et al.).
    For modalities including a photoclare dye, the color formation and targeting characteristics of the photoclare dye vary depending on a variety of factors including, for example, acid strength, dielectric constant, polarity, oxygen content, and moisture content in the atmosphere. . However, the bleaching properties of the dye can be readily determined by irradiating the composition and evaluating its color change. The photoclare dye is, in general, at least partially soluble in a hardenable resin.
    Photocleavable dyes include, for example, cane rose, methylene violet, methylene blue, fluorescein, eosin yellow, eosin Y, ethyleneosine, bluish eosin, eosin B, erythrosine B, yellowish erythrosine blend, toluidine blue, 4 ', 5'dibromofluorescein, and their combinations.
    The color change can be initiated by actinic radiation as provided by a dental curing lamp that emits visible or near-infrared (IR) light for a sufficient period of time. The mechanism that initiates the color change in the compositions can be separated from, or occur simultaneously with, the hardening mechanism that hardens the resin. For example, a composition can harden when polymerization is initiated chemically (e.g. redox initiation) or thermally, and the color change from an initial color to a final color can occur subsequent to curing under exposure to actinic radiation.
    Optionally, the compositions can contain solvents (for example propanol,
    36/54 ethanol), ketones (eg acetone, methyl ethyl ketone), esters (eg ethyl acetate), other non-aqueous solvents (eg dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1-methyl-2-pyrrolidinone)), and Water.
    If desired, the compositions may contain additives such as indicators, dyes, pigments, inhibitors, accelerators, viscosity modifiers, wetting agents, buffering agents, radical and cationic stabilizers (eg BHT,) and other similar ingredients that will be evident to the skilled in the art.
    In addition, drugs or other therapeutic substances can optionally be added to the dental compositions. Examples include, but are not limited to, fluoride sources, bleaching agents, anti-caries agents (for example xylitol), calcium sources, phosphorus sources, remineralizing agents (for example calcium phosphate compounds), enzymes, breath fresheners, anesthetics, coagulating agents, acid neutralizers, chemotherapeutic agents, immune response modifiers, thixotropes, polyols, anti-inflammatory agents, microbicidal agents (in addition to the lipid antimicrobial component), fungicidal agents, xerostomy treatment agents, desensitizers, and the like , the type often used in dental compositions. Combinations of any of the additives mentioned above can also be used. The selection and quantity of any of the additives can be made by the person skilled in the art to obtain the desired results without undue experimentation.
    The curable dental composition can be used to treat a buccal surface like a tooth, as is known in the art. In some embodiments, the compositions can be hardened by curing after application of the dental composition. For example, when the curable dental composition is used as a restorative, as in a dental restoration, the method, in general, comprises applying the curable composition to a buccal surface (e.g. cavity); and cure the composition. In some embodiments, a dental adhesive may be applied prior to the application of the curable dental restoration material described herein. Dental adhesives are also typically hardened by curing concurrently with curing the highly charged dental restoration composition. The method for treating a buccal surface may comprise providing a dental article and adhering the dental article to a buccal surface (e.g. tooth).
    In other embodiments, the compositions can be hardened (for example polymerized) in dental articles before application. For example, a dental article, such as a crown, can be preformed from the curable dental composition described herein. Dental composite articles (e.g. crowns) can be made from the curable composition described herein by pouring the curable composition into contact with a mold and curing the composition. Alternatively, the dental composite article (eg crowns) can be produced initially by curing the composition, forming a
    37/54 raw block for milling prosthesis (mill blank) and, then, by mechanically machining the composition to form the desired article.
    Another method of treating a dental surface comprises providing a dental composition as described herein in which the composition is in the form of a malleable, self-supporting, curable (partially cured) structure having a first semi-finished shape; positioning the curable dental composition on a dental surface in a subject's mouth; adjust the shape of the curable dental composition; and hardening the curable dental composition. The adjustment can take place inside the patient's mouth or on a model outside the patient's mouth as described in US 7,674,850 (Karim et al.); incorporated herein by way of reference.
    Objectives and advantages are further illustrated by the following examples, but the specific materials and proportions thereof referred to in these examples, as well as other conditions and details, should not be interpreted to unduly limit this invention. Unless otherwise noted, all parts and percentages are given based on weight.
    Addition-Fraqmentation Monomer Synthesis (AFM)
    Monomer)
    General procedures. All reactions were carried out in round bottom flasks or glass containers or vessels using unpurified commercial reagents.
    Materials. Commercial reagents were used as received. Dichloromethane, ethyl acetate, and toluene were obtained from EMD Chemicals Inc. (Gibbstown, NJ, USA). Glycidyl methacrylate, 4- (dimethylamino) pyridine, methacryloyl chloride, triphenylphosphine, 2,6-di-t-butyl-4-methylphenol, and dibutyltin dilaurate were obtained from Alfa Aesar (Ward Hill, MA, USA). 2-Isocyanatoethyl acrylate, 1,2-epoxy-3-phenoxypropane, and 1,2-epoxidecane were obtained from TCI America (Portland, OR, USA). Acryloyl chloride, triethylamine, and triphenylantimony were obtained from Sigma Aldrich (St. Louis, MO, USA). 4-Hydroxybutyl-acrylate-glycidylether was obtained from Nippon Kasei Chemical (Tokyo, Japan). Glycidyl acrylate was obtained from Polysciences Inc. (Warringotn, PA, USA). Mixture of methyl methacrylate oligomer was obtained according to the procedure detailed in Example 1 of US Patent No. 4,547,323 (Carlson, G. M.).
    Instrumentation. Proton nuclear magnetic resonance spectra (1H NMR) and carbon nuclear magnetic resonance spectra (13C NMR) were recorded on a 400 MHz spectrometer.
    Distillation of methyl methacrylate oligomer mixture distillation of methyl halfcrialate oligomer
    Distillation was carried out as described in Moad, C. L .; Moad, G .; Rizzardo, E .; and
    38/54
    Thang, S. H. Macromolecules, 1996, 29, 7717-7726, with details as follows:
    A 1 L round-bottom flask equipped with a magnetic stir bar was loaded with 500 g of methyl methacrylate oligomer mixture. The flask was coupled to a Vigreux column, a condenser, a distribution adapter, and four collecting flasks. With stirring, the distillation apparatus was placed under reduced pressure (33.3 Pa (0.25 mm Hg)). The oligomer mixture was stirred under reduced pressure at room temperature until the gas release (removal of methyl methacrylate monomer) had been predominantly decreased. The distillation flask was then heated to reflux in an oil bath to distill the oligomer mixture. The fractions isolated by this procedure are listed in table 1
    Table 1. Fractions of Distillation of the Methyl Methacrylate Oligomer Mixture
    Pressure (Pa Boiling point Mass
    Fraction (mm Hg)) (° C) (g) Approximate composition
    THE 33.3 (0.25) 59 63.27 Dimer B 12.0 (0.09) 47 115.97 Dimer Ç 13.3 (0.10) 60-87 25.40 dimer (-50-75%), oligomers(mainly trimer) D 13.3 (0.10) 87 15.20 dimer (-5%), oligomers(mainly trimer) AND 17.3 (0.13) 105 156.66 oligomers (trimer and higher) H methyl methacrylate dimer idolysis
    O O oo
    U _ Jl KOH7H 2 Q jl _ Jl * ° Alí ™ '-' AT ~ · 'diacid
    Hydrolysis of the dimer to diacid 1 was performed as described in Hutson, L .; Krstina, J .; Moad, G .; Morrow, G. R .; Postma, A .; Rizzardo, E .; and Thang, S. H. Macromolecules, 2004, 37, 4441-4452, with details as follows:
    A 1 L round-bottom flask, equipped with a magnetic stir bar, was charged with deionized water (240 mL) and potassium hydroxide (60.0 g, 1,007 mmol). the mixture was stirred until homogeneous. Methyl methacrylate dimer (75.0 g, 374.6 mmol) was added. The reaction flask was equipped with a reflux condenser and was heated to 90 ° C in an oil bath. After 17 hours, the reaction flask was removed from the oil bath and allowed to cool to room temperature. The reaction solution was acidified to a pH of approximately 1 using concentrated HCI. A white precipitate formed under acidification. The heterogeneous mixture was vacuum filtered and quickly washed twice with 50-100 ml of deionized water. The white solid was dried by passing air through the solid for approximately 4 hours. The white solid was then dissolved in
    39/54 approximately 1,750 mL of dichloromethane. Only a very small amount (less than a gram) of solid remained insoluble. The solution was allowed to stand for 24 hours. The dichloromethane solution was then filtered in vacuo to remove the undissolved white solid. The filtered dichloromethane solution was concentrated in vacuo to obtain a white solid. The soft solid was then dried under high vacuum to give diacid 1 (55.95 g, 325.0 mmol, 87%) as a white powder.
    Preparation of AFM-1
    AFM-1
    An amber flask of approximately 250 ml_ equipped with a magnetic stir bar was charged with glycidyl methacrylate (23.0 ml, 24.8 g, 174 mmol) and triphenylantimonium (0.369 g, 1.04 mmol). The reaction flask was covered with a plastic cap with two 16 gauge needles piercing through the cap to allow air to enter the reaction flask. With stirring, the mixture was heated to 100 ° C in an oil bath. Diacid 1 (15.0 g, 87.1 mmol) was added to the reaction flask in small portions over a period of 1.5 hours. After 21 hours, triphenylphosphine (0.091 g, 0.35 mmol) was added. The reaction was kept under stirring at 100 ° C. After an additional 6.5 hours the reaction was sampled, and analysis by 1H NMR was consistent with the desired product as a mixture of isomers and indicated consumption of glycidyl methacrylate. The reaction was cooled to room temperature to obtain AFM-1 as a clear, viscous, very light yellow material.
    Preparation of AFM-2 via Diol 2
    1. PhjSb
    2. Ph 3 P
    Preparation of Diol 2
    A glass vial of approximately 30 mL equipped with a magnetic stir bar was loaded with 1,2-epoxy-3-phenoxypropane (3.93 mL, 4.36 g, 29.0 mmol) and triphenylantimony (0.0593 g , 0.168 mmol). The reaction flask was closed with a plastic cap. With stirring, the mixture was heated to 100 ° C in an oil bath. The diacidol (2.50 g, 14.5 mmol) was added to the reaction in small portions over a period of 35 minutes. After 18 hours, triphenylphosphine (0.0162 g, 0.0618 mmol) was added. The reaction was kept under stirring at 100 ° C. After an additional 24 hours, the reaction was sampled and the 1 H NMR analysis was consistent with the desired product as a mixture of isomers. The reaction was cooled to room temperature to obtain diol 2 as a clear, colorless glassy material.
    40/54
    Preparation of AFM-2
    A 100 ml round-bottom flask equipped with a magnetic stir bar was loaded with diol 2 (4.956 g, 10.49 mmol) and dichloromethane (20 ml). With stirring, 2-isocyanatoethyl methacrylate (2.20 mL, 2.416 g, 20.98 mmol) was added. Dibutyltin dilaurate (3 drops from a glass pipette) was added to the clear and homogeneous solution. The reaction flask was closed with a plastic cap with a 16 gauge needle added to allow air to pass. After 72 hours, the reaction mixture was concentrated in vacuo to a clear viscous liquid. The liquid was transferred to a 25 ml amber flask using a small amount of dichloromethane. Air was bubbled through the viscous material to remove the solvent. Analysis by 1H NMR was consistent with the desired product as a mixture of isomers. AFM-2 (7.522 g, 9.63 mmol, 92%) was obtained as a clear, very viscous oil.
    Preparation of AFM-3
    O
    A 500 mL two-necked round-bottom flask equipped with a magnetic stir bar was loaded with AFM-1 (20.00 g, 43.81 mmol) and dichloromethane (160 mL). The mouths on the reaction flask were closed with plastic caps and a 16 gauge needle was added to each cap to open the reaction to air. The reaction was cooled to 0 ° C with stirring. Triethylamine (30.5 ml, 22.1 g, 219 mmol) and 4 (dimethylamino) pyridine (1.609 g, 13.17 mmol) were added. Methacryloyl chloride (17.0 mL, 18.4 g, 176 mmol) was added dropwise to the reaction mixture over a period of 40 minutes. The homogeneous, light yellow reaction was allowed to slowly warm up to room temperature. After 24 hours, the light yellow reaction solution was concentrated in vacuo. Ethyl acetate (400 mL) was added to the residue and the mixture was transferred to a 1 L separating funnel. The reaction flask was washed with aqueous hydrochloric acid (1N, 200 mL) and the aqueous hydrochloric acid solution was added to the
    41/54 separation funnel. The solutions were mixed well and the aqueous layer was removed. The organic solution was then washed twice with 200 ml of aqueous hydrochloric acid (1N), once with 200 ml of deionized water, three times with 200 ml of aqueous sodium hydroxide (1N), and once with 200 ml of deionized water. saturated aqueous sodium chloride solution. The organic solution was dried over sodium sulfate for 30 minutes and then filtered. 2 J 6-Di-t-butyl-4-methylphenol (0.011 g) was added, and the solution was concentrated in vacuo (bath temperature below 20 ° C) to a viscous solution. The concentrated solution was transferred to an amber flask using a small amount of dichloromethane to ensure quantitative transfer. Air was bubbled through the viscous material to remove the solvent. Analysis by 1H NMR was consistent with the desired product as a mixture of isomers. AFM-3 (23.44 g, 39.55 mmol, 90%) was obtained as a very viscous, very light yellow oil.
    Preparation of AFM-4
    A 250 ml 3-neck round-bottom flask was equipped with a magnetic stir bar. Diol 2 (6.86 g, 14.52 mmol) was dissolved in dichloromethane (25 ml) and added to the reaction flask. Five additional 5 ml portions of dichloromethane were used to ensure quantitative transfer of diol 2 and these washes were added to the reaction flask. The reaction flask was equipped with an addition funnel with a pressure equalizer capped with a plastic cap. The two other mouths of the reaction flask were also capped with plastic caps, and a 16 gauge needle was added to each one to allow the reaction to pass through the air. The reaction was cooled to 0 ° C with stirring. Triethylamine (10.0 mL, 7.26 g, 71.8 mmol) and 4 (dimethylamino) pyridine (0.532 g, 4.36 mmol) were added. A 37.3 wt% solution of methacryloyl chloride in toluene (16.28 g of solution, 6.07 g of methacryloyl chloride, 58.1 mmol) was added to the addition funnel. The methacryloyl chloride toluene solution was added dropwise to the reaction mixture over a period of 30 minutes. The reaction turned light yellow After 18 hours, the light yellow reaction solution was transferred to a 500 ml separating funnel using dichloromethane (200 ml). The organic solution was washed twice with 150 ml of aqueous hydrochloric acid (1N), once with 150 ml of deionized water, twice with 150 ml of aqueous sodium hydroxide (1N), and once with 200 ml of a solution saturated aqueous solution of sodium chloride. The organic solution was dried over sodium sulfate for 30 minutes, and was then filtered and concentrated in vacuo (bath temperature
    42/54 below 20 ° C) for a viscous solution. The concentrated solution was transferred to an amber flask using a small amount of dichloromethane to ensure quantitative transfer. Air was bubbled through the viscous material to remove the solvent. Analysis by 1H NMR was consistent with the desired product as a mixture of isomers. AFM-4 (8.463 g, 13.9 mmol, 96%) was obtained as a light yellow, very viscous oil.
    BisGMA (2,2-bis [4- {2-hydroxy-3-methacryloyloxy-propoxy) phenyljpropane (Sigma Aldrich, St. Louis, MO, USA)
    TEGDMA (triethylene glycol dimethacrylate, Sartomer Co., Inc., Exton, PA, USA)
    UDMA (diurethane dimethacrylate, CAS No. 41137-60-4, commercially available as Rohamere 6661-0, Rohm Tech, Inc., Malden, MA, USA)
    BisEMA6 (ethoxylated bisphenol A methacrylate as detailed in US Patent No. 6,030,606, available from Sartomer as “CD541)
    Procrilat (2,2-bis-4- (3-hydroxypropoxyphenyl) propane dimethacrylate, CAS 27689-29, prepared as described in WO 2006/020760)
    CAPA2125 IEM (refers to the reaction product of CAPA2125 (a polycaprolactonapoliol available from Solvay Chemical Company, Warrington, UK) and two equivalents of 2-isocyanatoethyl methacrylate, prepared essentially as described in US patent No. 6,506,816)
    GDMA-P (glycerol-dimethacrylate-phosphate 75% by weight) prepared as described in J. Dent. Res., 35, 8466 (1956), can also be prepared as described in example 2 of US patent No. 6,187,838) mixed with 25% by weight of TEGDMA)
    CPQ (camphoroquinone, Sigma Aldrich, St. Louis, MO, USA)
    EDMAB (ethyl 4- {N, N-dimethylamino) benzoate, Sigma Aldrich)
    DPIHFP (diphenyliodonium hexafluorophosphate, Alpha Aesar, Ward Hill, MA, USA)
    BHT (butylated hydroxytoluene, Sigma Aldrich)
    BZT (refers to 2- (2-hydroxy-5-methacryloxyethylphenyl) -2 / - / - benzotriazole, Ciba, Inc., Tarrytown, NY, USA)
    HEMA (2-hydroxyethyl methacrylate, Sigma-Aldrich)
    Tris- (2-hydroxyethyl) isocyanurate (TCI America, Portland, OR, USA)
    DCC (dicyclohexyl-carbodiimide, TCI)
    YbF 3 (ytterbium fluoride, Treibacher, Germany)
    MEHQ (hydroquinone-monomethyl-ether, Sigma-Aldrich) “Irgacure 819” (phosphine oxide photoinitiator, available from Ciba Specialty Chemicals Corp., Tarrytown, NY, USA)
    Zr / Si charge (with treated surface, one hundred parts of 0.6-0.9 micrometer medium-sized zirconia-silica charge were mixed with water
    43/54 deionized at a solution temperature of between 20 and 30 ° C, and the pH is adjusted to 3-3.3 with trifluoroacetic acid (0.278 part). Silane A-174 (SILQUEST A-174, gamma methacryloxypropyltrimethoxysilane, Crompton Corporation, Naugatuck, CT, USA) was added to the slurry in an amount of 7 parts and the blend is mixed for 2 hours. At the end of 2 hours, the pH is neutralized with calcium hydroxide. The load is dried, crushed and sieved through a 74 or 100 micrometer sieve.)
    Zr / Si nanoaggregation charge (silane-treated zirconia-silica nanoaggregation charge prepared essentially as described in US patent No. 6,730,156 (preparation example A (line 51-64) and example B (column 25 line 65 to column 26 row 40))
    75 nm silica charge (prepared as described for charge A in column 22 of US patent No. 7,393,882)
    20 nm silica filler (silica nanometer size treated with silane having a nominal particle size of approximately 20 nanometers, prepared essentially as described in US Patent No. 6,572,693 B1 (column 21, lines 63-67 for particle loading nanometer size, Type # 2))
    Aerosil R812S (vaporized silica, Degussa, Germany)
    Isocyanurate trimer - Synthesis of tri-hydroxyethylisocyanurate phthalate Tris HEMA
    Phthalic anhydride (57.0 g, 0.385 mol, CAS # 85-33-9, Alfa Aesar, lot G30T004), 4 (dimethylamino) pyridine (DMAP, 4.9 g, 0.04 mol, CAS # 1122-58- 3, Alfa Aesar, lot L125009), 2-hydroxyethyl methacrylate (HEMA, 50.9 g, 0.391 mol, and butylated hydroxytoluene (BHT, 0.140 g) were loaded into a 2-liter 3-bottle reaction flask equipped with a mechanical stirrer, a thermocouple connected to a temperature controller, a stream of dry air passing through a T-connection into the reactor then to an oil bubbler, and a heating mantle. With continuous stirring, the contents of the flask were heated to 95 ° C, near which all components dissolved and a clear liquid was obtained Heating at 95 ° C and stirring was continued for 5 hours Heating was turned off and the contents of the flask were allowed to cool to room temperature while still stirring under dry air, acetone (250 mL) was added followed by tris- (2-hydroxyethyl) isocyanur act (33.58 g, 0.158 mol, from TCI). The heating blanket was replaced by an ice bath, where the mixture was cooled to 0-5 ° C. A prepared solution of dicyclohexylcarbodiimide (DCC, 81 g, 0.393 mol) in 120 ml of acetone was added to a 500 ml addition funnel that was positioned between the reaction flask and the dry air inlet. The DCC solution was added slowly to the continuously stirred reaction mixture at a rate at which the temperature of the temperature reaction mixture would not exceed 10 ° C. After the complete addition of the DCC solution, the reaction was stirred in the ice bath for 2 hours at room temperature overnight. On day 2, the solid formed was
    44/54 removed by vacuum filtration and the residue was concentrated on a rotary evaporator in a bath at 40-45 ° C. The residue was dissolved in 300 ml of 2: 1 by volume ethyl acetate: hexanes solution. The obtained solution was extracted with 200 ml of 1.0 N HCI, 200 ml of 10% aqueous solution, 200 ml of H 2 O, and 200 ml of brine. The organic layer was concentrated on a rotary evaporator with a 40 ° C bath. Additional drying was carried out under a vacuum pump at 50 ° C for 3 hours with air flowing into the product at all times to give an almost colorless cloudy viscous liquid.
    The refractive index was measured with a value of 1.5386. Using NMR it was determined that the liquid was the product shown in the following reaction scheme. The calculated molecular weight of the final portrayed product determined was 1,041 g / mol.
    The calculated molecular weight of the determined linker was 220 g / mol.

    DMAP
    95 ° C, 5 h at -
    DCC
    Aeetona
    Recovery ο ο γγ 2 o
    Synthesis of TGP-IEM
    General Procedure T. Reaction of a Diol Precursor with Components
    Epoxides Using TEAA as Catalyst
    For example, TCD and GMA alcohol, as the epoxy component (s) functional reagent (s), are mixed with stirring with for example cyclohexane. 1.5% by weight of TEA and 1.5% by weight of GAA (which relate to the mass of the sum of all reagents, to form TEAA locally), 1,000 ppm HQ, 200 ppm BHT, and 200 ppm HQME are added with stirring. Then the mixture is heated while stirring at a temperature of about 70 ° C until the completion of the addition reaction (measured via 1H-NMR: no sign of residual epoxyl groups was detected). Optionally, 3 to 5% by weight of MSA are slowly added while stirring and the addition is continued for about 60 min at about 70 ° C. The mixture is then allowed to cool to room temperature with stirring. The upper phase of cyclohexane is separated from the lower viscous oily phase, if any. The separated cyclohexane phase is washed once with water, then
    45/54 extracted twice with 2N NaOH solution, then once washed with water, then dried with anhydrous Na 2 SO 4 . After filtration, the filtrate is again filtered through basic alumina. 100 ppm BHT and 100 ppm HOME are added to the filtrate. Then, the solvent is removed under vacuum while air is bubbled through the crude sample.
    According to general procedure 1, 100 g of TCD alcohol, 155 g of GP and 3.00 g of MSA were reacted. 253 g of TGP (509 mmol, 99%) were isolated as yellow oil. According to general procedure 4, 100 g of TGP and 59.4 g of EMI were reacted. 158 g of TGP-IEM (196 mmol, 99%) were isolated as yellow oil: η = 1400 Pa.s, n D 20 = 1.531.
    Synthesis of TTEQ-IEM
    General Procedure 2: Reaction of a Diol Precursor as with Mixtures Containing
    Epoxy Components (eg EO in THF) Using BF / THF as Catalyst
    For example, TCD alcohol is diluted with anhydrous THF, then BF 3 * THF is added with stirring. EO gas is added while stirring so that the temperature of the reaction mixture does not exceed about 30-40 ° C. After the completion of the addition of EO, stirring is continued at room temperature for about 30 min. 13% by weight of water (which refers to the sum of the proportions of the reactive educts) is added after about 30 min while, with stirring, 13% by weight of basic alumina is also added. After about 60 min of further stirring, 13% by weight of a solution of sodium methanolate in methanol (30% in methanol) is added. The suspension is then stirred at room temperature for about 12 h. After filtration, the solvent is removed in vacuo.
    According to general procedure 2, 300 g of TCD alcohol, 64.6 g of EO, 600 g of THF and 37.9 g of BF 3 * THF were reacted. 429 g of TTEO were isolated as colorless oil. According to general procedure 4, 55.3 g of TTEO and 54.7 g of EMI were reacted. 100 g of TTEO-IEM (95%) were isolated as colorless oil: η = 45 Pa.s, n D 20 = 1.503.
    Synthesis of TTEO-MA:
    General Procedure 3: Diol Precursor Reaction such as alcohol
    TÇD with Mixtures Containing Epoxide (eg EO in THF) Using BF 3 * THF as Catalyst
    For example, TCD alcohol is diluted with anhydrous THF, then BF 3 * THF is added with stirring. EO gas is added under stirring so that the temperature of the reaction mixture does not exceed about 30-40 ° C. After the completion of the addition of EO, stirring is continued at room temperature for about 30 min. 13% by weight of water (which refer to the sum of the proportions of the reactive educts) are added, after about 30 min with agitation 13% by weight of basic alumina are also added. After about 60 min of further stirring, 13% by weight of a solution of sodium methanolate in methanol (30% in methanol) is added. The suspension is then stirred at room temperature for about 12 h. After filtration, the solvent is removed in vacuo.
    46/54
    According to the general procedure 3 300 g of TCD alcohol, 64.6 g of EO, 600 g of THF, and 37.9 g of BF 3 * THF were reacted. 429 g of TTEO were isolated as colorless oil. According to the general procedure 4 213 g TTEO, 161 g MA, 44.8 mg BHT, 121 mg HOME, 89.6 mg methylene blue, and 12.8 g MSA were reacted using hexane as solvent. 237 g of TTEO-MA (67%) were isolated as a colorless liquid: η = 0.1 Pa.s, n D 20 = 1.499.
    Test Methods
    Stress Test Method
    To measure the development of stress during the curing process, a notch was machined from a 15mm x 8mm x 8mm rectangular aluminum block, as shown in figure 1. The notch was 8mm long, 2.5 mm deep, and 2 mm side by side, and it was located 2 mm from an edge, thus forming a 2 mm wide aluminum cusp adjacent to a 2 mm wide cavity containing dental compositions being tested. A differential transducer of linear variation (Model GT 1000, used with an analog amplifier E309, both from RDP Electronics, United Kingdom) was positioned as shown to measure the displacement of the tip of the cusp as the dental composition photocured at room temperature. Before the test, the notch in the aluminum block was sandblasted using “Rocatec Plus Special Surface Coating Blasting Material” (3M ESPE), treated with “RelyX Ceramic Primer” (3M ESPE), and finally treated with a dental adhesive, “ Adper Easy Bond ”(3M ESPE).
    The notch was completely filled with the mixtures shown in the tables, which equaled approximately 100 mg of material. The material was irradiated for 1 minute with a dental curing lamp (Elipar S-10, 3M ESPE) positioned almost in contact (<1 mm) with the material inside the notch, then the displacement of the cusp in microns was recorded 9 minutes after turning off the lamp.
    Watts Contraction Test Method
    The Watts contraction test method (Watts) measures the contraction of a test sample in terms of volumetric change after curing. Sample preparation (90 mg uncured composite test sample) and test procedure were performed as described in the following reference: Determination of Polymerization Shrinkage Kinetics in VisibleLight-Cured Materials: Methods Development, Dental Materials ”, October 1991, pages 281286. Results are reported as% negative contraction.
    Diametral Tensile Strength Test Method (DTS)
    The diametrical tensile strength of a test sample was measured according to the following procedure. An uncured composite sample was injected into a 4 mm glass tube (internal diameter); the tube was capped with silicone rubber plugs. The tube was axially compressed at approximately 2.88 kg / cm 2 of pressure
    47/54 for 5 minutes. The sample was then light cured for 80 seconds by exposure to XL 1500 dental curing light (3M Company, St. Paul, MN, USA), followed by irradiation for 90 seconds in a Kulzer UniXS curing box (Heraeus Kulzer GmbH, Germany). The cured samples were allowed to stand for 1 hour at about 37 ° C / relative humidity above 90%. The sample was cut with a diamond saw to form discs about 2.2 mm thick, which were stored in distilled water at 37 ° C for about 24 hours before testing. Measurements were performed on an Instron tester (Instron 4505, Instron Corp., Canton, MA, USA) with a 10 kilonewton (kN) load cell at a tensile speed of mm / minute according to ISO Specification 7489 (or American Dental Association (ADA) Specification No. 27). Six disks of cured samples were prepared and measured with the results reported in MPa as the average of the six measurements.
    Barcol's Hardness Test Method
    The Barcol hardness of a test sample was determined according to the following procedure. An uncured composite sample was cured in a 2.5-mm or 4-mm thick TEFLON mold interposed between a sheet of polyester film (PET) and a glass slide for 20 seconds and cured with a curing light. dental ELI PAR Freelight 2 (3M Company). After irradiation, the PET film was removed and the hardness of the sample at both the top and bottom of the mold was measured using a Barber-Coleman Printer (a hand held hardness tester); Model GYZJ 934-1; Barber-Coleman Company, Industrial Instruments Division, Lovas Park, Ind.) Equipped with an indenter. The Barcol hardness values of the top and bottom were measured 5 minutes after exposure to light.
    Depth of Curing Test Method
    The curing depth was measured by filling a 10 mm stainless steel mold cavity with the composite, covering the top and bottom of the mold with sheets of polyester film, pressing the sheets to obtain a level composition surface, positioning the filled mold on a white background surface, radiating the dental composition for 20 seconds using a dental curing light (3M Dental Products Curing Light 2500 or 3M ESPE Elipar FreeLight2, 3M ESPE Dental Products), separating the polyester films on each side from the mold, carefully removing (by scraping) the materials from the bottom of the sample (ie, the side that has not been irradiated with dental curing light), and measuring the thickness of the remaining material within the mold. The reported depths are the actual cured thickness in millimeters divided by 2.
    Flexural Strength and Flexural Module Test Method
    A paste sample was extruded into a 2 mm X mm X 25 mm quartz glass mold forming a test bar. The material was then cured through
    48/54 mold using 2 standard dental curing lights (3M ESPE XL2500 or 3M ESPE XL3000). The samples were cured by placing a light in the center of the sample bar, curing for 20 s, then simultaneously curing the ends of the bar for 20 s, inverting and repeating.
    The samples were stored submerged in distilled water at 37 ° C before the test (16 to 24 h). Flexural strength and flexural module of the bars were measured on an Instron tester (Instron 4505 or Instron 1123, Instron Corp., Canton, Mass., USA) according to ANSI / ADA (American National Standard / American Dental Association) Specification n ° 27 (1993) at a traction speed of 0.75 mm / minute. The results were reported in megapascals (MPa).
    Test Method and Compressive Strength
    The compressive strength of a test sample was measured according to the following procedure. An uncured composite sample was injected into a 4 mm glass tube (internal diameter); The tube was then capped with silicone rubber plugs; and, then, the tube was axially compacted at a pressure of approximately 2.88 kg / cm 2 for 5 minutes. The sample was then light cured for 80 seconds by exposure to XL 1500 dental curing light (3M Company, St. Paul, MN, USA), followed by irradiation for 90 seconds in a Kulzer UniXS curing box (Heraeus Kulzer GmbH, Germany). The cured samples were allowed to stand for 1 hour at about 37 ° C / relative humidity above 90% and then were cut with a diamond saw to form 8 mm long cylindrical plugs to measure the compressive strength. The buffers were stored in distilled water at 37 ° C for about 24 hours before testing. Measurements were performed on an Instron tester (Instron 4505, Instron Corp., Canton, MA, USA) with a 10 kilonewton (kN) load cell at a traction speed of 1 mm / minute according to ISO Specification 7489 ( or American Dental Association (ADA) Specification No. 27). Five cylinders of cured samples were prepared and measured with the results reported in MPa as the average of the five measurements.
    Shear Resistance Test Method for Enamel or Dentin
    Teeth preparation: Bovine incisor teeth, free of mold tissue, were embedded in circular acrylic discs. The soaked teeth were stored in water in a refrigerator before use. In preparation for the adhesive test, the embedded teeth were sanded to expose a flat dentin or enamel surface using a granulation sandpaper 120 mounted on a lapping wheel. Additional sanding and polishing of the dental surface was done with the use of 320 grain sanding paper on a lapping wheel. The teeth were continuously rinsed with water during the sanding process. The polished teeth were stored in deionized water and used for testing within 2 hours after polishing. The teeth were allowed to heat in a fire to 36 ° C
    49/54 to between room temperature (23 ° C) and 36 ° C before use.
    Teeth treatment: An adhesive reinforcement seal (having an opening of
    150 micrometers thick and 5 mm in diameter) was applied to the prepared dental surfaces and a thin layer of the composite was applied with an applicator brush inside the opening of the reinforcing adhesive seal, brushing for 20 s. The composite layer was cured for 20 s using an Elipar S10 curing light (3M ESPE). Next, a Teflon mold having an opening (2 mm thick by 5 mm in diameter) was placed on the cured composite layer, filled with more of the same composite, and the composite was cured for 20 s using the cure S10. This formed a cured composite button adhered to the prepared dental surface.
    Adhesive bond strength test: The adhesive strength of a cured test example was assessed by mounting (described above) on a bracket attached to the grip of an INSTRON test machine (Instron 4505, Instron Corp. Canton, Mass., USA) with the polished dental surface oriented parallel to the pulling direction. An orthodontic wire loop (0.44 mm in diameter) was positioned around the composite button adjacent to the polished dental surface. The ends of the orthodontic wire were fixed on the pulling jaw of the INSTRON appliance and pulled at a traction speed of 2 mm / min, thus subjecting the adhesive bond to the shear stress. The force in kilograms (kg) at which the bond broke was noted, and that number was converted to a force per unit area (units of kg / cm 2 or MPa) using the known surface area of the button. Each reported enamel adhesion or dentin adhesion value represents the average of 4 to 5 repetitions.
    Paste Compositions
    The components shown in the tables were measured and mixed together until uniform mixing was obtained.
    TTEO-IEM Trimerisocyanurate πΕΟ-BAD CPQ EDMAB DPIHFP Chargeof Zr / Si AFM-1 AFM-2 % inweight ofAFM'sresinonly CE1 9,599 9,655 1,951 0.037 0.209 0.108 78.44 1 9,547 9.54 1,915 0.035 0.211 0.106 78.43 0.21 0.99 2 9,422 9,383 1.89 0.039 0.207 0.104 78.42 0.54 2.48 3 9,161 9.204 1.817 0.032 0.203 0.101 78.42 1.06 4.91 4 8,947 8,921 1,789 0.032 0.196 0.101 78.42 1.59 7,371 CE2 9,995 10,162 1,055 0.032 0.216 0.11 78.43 5 9,922 10.052 1,034 0.037 0.214 0.106 78.42 0.21 0.99 6 9,777 9.9 1.003 0.037 0.207 0.106 78.44 0.53 2.46 7 9,517 9,622 1,022 0.032 0.203 0.101 78.43 1.07 4.97
    50/54
    8 9,269 9,383 0.989 0.037 0.198 0.099 78.43 1.6 7.409 TTEO-IEM Trimerisocyanurate TTEO-BAD CPQ EDMAB DPIHFP Chargeof Zr / Si AFM-3 AFM-4 % inweight ofAFM'sresinonly CE3 9,925 10.063 1,039 0.032 0.181 0.092 78.67 9 9,822 9,959 1,028 0.032 0.179 0.09 78.68 0.21 0.98 10 9,659 9,796 1,011 0.03 0.177 0.087 78.71 0.53 2.48 11 9,425 9,558 0.987 0.03 0.173 0.085 78.69 1.05 4.93 12 9,195 9,323 0.962 0.03 0.169 0.083 78.66 1.58 7.39 CE4 9,907 10.043 1,055 0.036 0.209 0.109 78.64 13 9.806 9,943 1,045 0.038 0.211 0.105 78.64 0.21 0.98 14 9,661 9,794 1,027 0.038 0.205 0.109 78.64 0.52 2.45 15 9.409 9,539 1.002 0.038 0.216 0.105 78.64 1.05 4.92 16 9,166 9,292 0.976 0.034 0.209 0.107 78.64 1.58 7.38
    TGP-IEM Isocyanurate trimer TTEO-BAD CPQ EDMAB DPIHFP ChargeinZr / Si AFM-1 % by weight of resin AFM only CE5 9.6 9,655 1,951 0.037 0.209 0.108 78.44 17 9.55 9.54 1,915 0.035 0.211 0.106 78.43 0.21 0.99 18 9.42 9,383 1.89 0.039 0.207 0.104 78.42 0.54 2.48 19 9.16 9.204 1.817 0.032 0.203 0.101 78.42 1.06 4.91 20 8.95 8,921 1,789 0.032 0.196 0.101 78.42 1.59 7,371
    The test results are reported as follows. For each test the mean is reported followed by the standard deviation in parentheses. The number of samples used 5 for each test is reported in the first line as "n". Thus, n = 3 means that three samples were tested.
    Tension,deflectionone (n = 3) Contractionof Watts,negative%(n = 5) Resistance [Barcol tensile strength, Hardness ofBarcol,2.5 mm,bottom(n = 6) Hardness ofBarcol,4.0 mm,top (n = 6) Hardness ofBarcol,4.0 mm,background (n = 6) Depthcuring time, mm(n = 3) diametral,Mpa (n = 6) 2.5 mm,top (n = 6) CE1 2.01(0.11) 1.51 (0.04) 87.8 (5.2) 67.5 (2.5) 65.7 (2.1) 67.7 (2.6) 72.8 (1.6) 5.04 (0.11) 1 1.57(0.14) 1.50 (0.05) 81.6 (3.9) 66.3 (1.4) 66.5 (2.6) 66.8 (1.3) 69.3 (1.2) 4.84 (0.22) 2 0.96 1.19 (0.06) 84.0 (7.8) 40.5 (3.0) 49.7 (5.0) 50.7 (1.2) 53.5 (3.0) 4.43 (0.04)
    51/54
    (0.04) 3 0.96(0.02) 1.15 (0.01) 84.3 (3.0) 41.5 (3.3) 47.2 (3.0) 50.7 (1.4) 49.7 (0.8) 4.29 (0.08) 4 0.77(0.05) 1.15 (0.05) 85.4 (7.7) 43.5 (5.8) 39.0 (5.9) 46.8 (1.5) 50.3 (3.4) 4.21 (0.07) CE2 2.02(0.13) 1.42 (0.04) 88.3 (2.1) 71.8 (0.8) 66.5 (1.8) 71.0 (1.1) 68.5 (0.8) 5.08 (0.03) 5 1.76(0.08) 1.31 (0.02) 89.2 (5.4) 66.2 (0.8) 67.3 (2.1) 69.3 (0.8) 68.5 (2.4) 4.74 (0.09) 6 1.50(0.11) 1.24 (0.05) 86.2 (3.2) 58.8 (1.7) 64.0 (1.6) 64.5 (1.1) 65.3 (0.8) 4.58 (0.05) 7 0.86(0.03) 1.08 (0.04) 81.7 (5.3) 50.8 (1.5) 53.5 (2.1) 54.2 (1.8) 56.2 (2.3) 4.39 (0.05) 8 0.54(0.06) 0.98 (0.04) 79.2 (3.6) 29.0 (7.1) 36.3 (2.8) 41.2 (1.5) 44.3 (2.4) 3.98 (0.11) CE3 1.78(0.16) 1.39 (0.03) 87.9 (12.7) 66.7 (1.8) 71.0 (1.6) 69.5 (1.9) 70.7 (1.2) 4.55 (0.14) 9 1.82(0.12) 1.35 (0.02) 85.9 (8.3) 64.7 (1.2) 66.2 (1.9) 66.0 (1.3) 69.5 (1.1) 4.50 (0.06) 10 1.42(0.17) 1.31 (0.04) 89.7 (6.7) 61.0 (2.1) 65.0 (0.9)... 66.5 (1.6) 68.3 (1.4) 4.35 (0.04) 11 1.16(0.06) 1.21 (0.03) 87.6 (9.3) 54.5 (2.4) 55.5 (1.9) 59.0 (2.6) 65.2 (1.5) 3.96 (0.10) 12 0.95(0.04) 1.14 (0.01) 85.2 (16.9) 49.0 (1.8) 54.8 (0.8) 54.3 (1.4) 55.2 (2.3) 3.80 (0.10) CE4 1.71(0.06) 1.36 (0.02) 76.9 (3.8) 64.2 (0.8) 69.7 (2.4) 65.3 (1.2) 70.0 (1.3) 4.38 (0.06) 13 1.68(0.01) 1.40 (0.07) 82.7 (6.5) 66.0 (1.4) 69.3 (0.8) 65.5 (1.1) 68.7 (1.9) 4.37 (0.12) 14 1.44(0.02) 1.35 (0.01) 84.3 (3.8) 60.3 (1.5) 67.8 (1.0) 64.3 (1.0) 65.7 (1.2) 4.24 (0.15) 15 0.98(0.08) 1.24 (0.04) 84.1 (8.5) 54.8 (2.5) 58.5 (1.1) 56.3 (2.7) 59.8 (1.2) 3.85 (0.00) 16 0.88(0.03) 1.17 (0.02) 78.2 (6.0) 51.7 (0.8) 54.3 (1.6) 49.7 (1.8) 55.3 (1.0) 3.66 (0.04) CE5 1.35(0.17) 1.28 (0.05) 78.5 (3.2) 65.3 (0.8) 69.5 (2.3) 66.5 (3.4) 61.3 (3.7) 4.70 (0.05) 17 1.25(0.15) 1.24 (0.06) 73.8 (6.5) 64.7 (1.6) 62.7 (2.0) 59.2 (1.3) 62.7 (1.6) 4.62 (0.14) 18 1.10 1.17 (0.03) 74.0 (6.6) 57.7 (1.6) 61.3 (1.2) 57.3 (2.2) 57.7 (2.0) 4.35 (0.07)
    52/54
    (0.16) 19 0.62(0.08) 1.05 (0.01) 78.0 (3.1) 51.8 (1.6) 51.2 (4.6) 53.7 (1.4) 49.0 (4.1} 4.19 (0.03) 20 0.55(0.09) 1.03 (0.02) 72.6 (6.8) 53.2 (2.1) 51.2 (1.7) 44.3 (3.4) 39.2 (5.4) 4.10 (0.05)
    The test results show the improved properties of examples 1-20, comprising addition-fragmentation materials, in comparison with CE1-CE5 that do not have the inclusion of an addition-fragmentation material. In particular, as the concentration of addition-fragmentation materials increases, the compositions exhibit reduced stress and reduced Watts contraction while maintaining sufficient resistance to diametrical tensile strength, Barcol hardness and curing depth.
    Dental compositions were also prepared in which an addition-fragmentation monomer was added in a conventional dental composition. Compositions CE6 and 21 also contained 0.108 DFIHFP and 0.03 BHT.
    BisGMA TEGDMA UDMA BisEMAÔ CPQ EDMAB BZT AFM-1 Nanp load Zr / Si clustering % by weight of resin AFM only CE6 5.161 1,175 7.226 7.226 0.04 0.215 0.32 78.5 21 4,774 1,089 6.684 6.684 0.04 0.215 0.32 1.61 78.5 7.73
    The test results are reported as follows. For each test the mean is reported followed by the standard deviation in parentheses. The number of samples used for each test is reported in the first line as "n".
    Stress, deflection one (n = 2) Watts contraction, negative% (n = 5) tensile strengthdiametrical, Mpa (n = 4-6) Barcol Hardness,2.5 mm, top (n = 6) Barcol Hardness,2.5 mm, bottom (n = 6) Curing depth, mm (n = 3) CE6 4.08(0.18) 1.87 (0.04) 75.9 (3.0) 76.3 (1.4) 78.8 (1.5) 4.68 (0.10) 21 2.91(0.28) 1.77 (0.04) 71.2 (9.4) 76.0 (2.6) 73.7 (1.7) 4.24 (0.05)
    Compositions CE7-26, as follows, also contained 0.06 CPQ, 0.108 DFIHFP, 0.216 EDMAB, 0.03 BHT, 0.22 BZT, and 3.0 YbF3.
    BisGMA TEGDMA Procrilat COVER2125IEM AFM-1 ChargeinZr / Si Zr / Si nano cluster charge Chargeinsilicain75 nm Silica charge of20 nm % inresin AFM weight only CE7 9.17 5.51 19.63 1.06 54.22 4.52 2.26 22 8.71 5.23 18.65 1.01 1.77 54.22 4.52 2.26 5 23 8.44 5.07 18.06 0.98 2.83 54.22 4.52 2.26 8 24 8.25 4.96 17.66 0.96 3.54 54.22 4.52 2.26 10.01 25 7.79 4.68 16.68 0.9 5.3 54.22 4.52 2.26 14.98 CE8 9.17 5.5 19.63 1.06 54.22 4.52 2.26 26 8.71 5.23 18.65 1.01 1.77 54.22 4.52 2.26 5
    The test results are reported as follows. For each test the mean is reported followed by the standard deviation in parentheses. The number of samples used
    53/54 for each test is reported in the first line as “n”.
    Stress, deflection one (n = 2) Diametrical tensile strengthMPa (n = 4-6) Resistanceflexural,MPa (n = 6) Flexural Flexural module, MPa (n = 6) Compressive strength, MPa (n = 5) CE7 4.14(0.49) 63.3 (6.7) 127 (8.7) 7309 (146) 342 (25.5) 22 2.39(0.05) 55.9 (8.6) 120 6157 339 (9.4) 23 1.63(0.10) 53.3 (7.6) 103 (6.0) 5539 (77) 325 (10.8) 24 1.55(0.03) 62.8 (4.2) 101 (6.6) 5187 (200) 338 (4.5) 25 0.8 (0.03) 59.7 (8.4) 86 (14.5) 3894 (198) 323 (3.2) CE8 4.19(0.19) Not tested 26 2.72(0.04) Not tested
    In some embodiments, dental compositions comprising conventional dental monomers and addition-fragmentation materials exhibited higher stress deflection results (for example> 2.0) than in examples 1-20, comprising addition-fragmentation and monomer materials low contraction. However, the inclusion of an addition-fragmentation material still substantially reduced stress deflection compared to substantially the same composition without such addition-fragmentation material.
    Component Examplecomparative Example 27 Example 28 Example 29 AFM-1 0.00 2.00 3.00 4.00 UDMA 7.60 7.45 7.37 7.30 HEMA 11.50 11.27 11.16 11.04 BisGMA 3.80 3.72 3.69 3.65 BisEMA6 3.80 3.72 3.69 3.65 GDMA-P 11.60 11.37 11.25 11.14 MEHQ 0.023 0.023 0.022 0.022 CPQ 0.115 0.113 0.112 0.110 EDMAB 0.92 0.90 0.89 0.88 Irgacure 819 0.38 0.37 0.37 0.36 Zr / Si charge 59.40 58.21 57.62 57.02 Aerosil R812S 0.99 0.97 0.96 0.95
    Results
    Adhesion inenamel, MPa (standard deviation) Adhesion indentin, MPa(standard deviation) Resistance tocompression, MPa(standard deviation) Diametrical tensile strength, MPa (standard deviation) Examplecomparative 9.4 (5.0) 11.9 (3.8) 345 (31) 80 (10) Example 27 11.3 (1.2) 9.9 (2.6) 337 (20) 83 (4) Example 28 Not tested Not tested 352 (32) 81 (10) Example 29 8.5 (1.7) 6.5 (3.0) 369 (20) 22 (8)
    Hardness ofBarcol, 2.0 mm, top (offsetstandard) Hardness ofBarcol, 2.0 mm, bottom (deviationstandard) Stress, deflection one (standard deviation) Examplecomparative 78 (0) 78 (0) 7.16 (0.11)
    54/54
    Example 27 78 (0) 78 (0) 5.46 Example 28 78 (0) 78 (0) 4.39 (0.20) Example 29 75 (1) 75 (1) 2.92 (0.15)
    * ELIPAR XL 3000 curing light was used in place of ELIPAR Freelight 2
    1/2
    权利要求:
    Claims (10)
    [1]
    CLAIMS:
    1. Dental composition FEATURED for understanding: an addition-fragmentation agent of formula:
    on what:
    R 1 , R 2 and R 3 are each independently Zm-Q-, a (hetero) alkyl group or (hetero) aryl group with the proviso that at least one of R 1 , R 2 and R 3 is Zm-Q-;
    Q is a linking group that has a valence of m +1;
    Z is an ethylenically unsaturated polymerizable group; m is 1 to 6;
    each X 1 is independently -O- or -NR 4 -, where R 4 is H or C V C 4 alkyl; and n is 0 or 1;
    at least one monomer comprising at least two ethylenically unsaturated groups; and inorganic oxide charge.
    [2]
    2. Dental composition according to claim 1, CHARACTERIZED by the fact that the addition-fragmentation agent comprises at least two ethylenically unsaturated end groups.
    [3]
    3. Dental composition, according to claim 1, CHARACTERIZED by the fact that Z comprises functional groups vinyl, vinyloxy, (meth) acryloxy, (meth) acrylamide, styrenic and acetylenic.
    [4]
    4. Dental composition, according to claim 1, CHARACTERIZED by
    [5]
    5. Dental composition according to claim 1, characterized by the fact that Q is alkylene or hydroxyl-substituted alkylene or aryloxy-substituted alkylene or alkoxy-substituted alkylene.
    2/2
    [6]
    6. Dental composition according to any one of claims 1 to 5, CHARACTERIZED by the fact that the ethylenically unsaturated groups of the monomer are (meth) acrylate groups.
    [7]
    7. Dental composition according to any one of claims 1 to 6, 5 CHARACTERIZED by the fact that the monomer is an aromatic monomer having a refractive index of at least 1.50.
    [8]
    8. Dental composition according to any one of claims 1 to 7, CHARACTERIZED by the fact that the monomer is a low volume contraction monomer.
    [9]
    9. Dental composition according to any one of claims 1 to 8,
    CHARACTERIZED by the fact that the dental composition comprises at least one (meth) acrylate monomer selected from ethoxylated bisphenol A dimethacrylate (BisEMA6), 2-hydroxyethyl methacrylate (HEMA), bisphenol-A-diglycidyl dimethacrylate (bisGMA), dimethacrylate urethane (UDMA), triethylene glycol dimethacrylate (TEGDMA),
    [10]
    15 glycerol dimethacrylate (GDMA), ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate (NPGDMA), polyethylene glycol dimethacrylate (PEGDMMA), and mixtures thereof.
    10. Dental composition according to any one of claims 1 to 9, CHARACTERIZED by the fact that the inorganic oxide filler comprises nanoparticles.
    1/1
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    同族专利:
    公开号 | 公开日
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    EP2965742B1|2020-09-09|
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    法律状态:
    2017-11-07| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2017-12-12| B07D| Technical examination (opinion) related to article 229 of industrial property law|Free format text: DE ACORDO COM O ARTIGO 229-C DA LEI NO 10196/2001, QUE MODIFICOU A LEI NO 9279/96, A CONCESSAO DA PATENTE ESTA CONDICIONADA A ANUENCIA PREVIA DA ANVISA. CONSIDERANDO A APROVACAO DOS TERMOS DO PARECER NO 337/PGF/EA/2010, BEM COMO A PORTARIA INTERMINISTERIAL NO 1065 DE 24/05/2012, ENCAMINHA-SE O PRESENTE PEDIDO PARA AS PROVIDENCIAS CABIVEIS. |
    2017-12-26| B07B| Technical examination (opinion): publication cancelled|Free format text: REFERENTE AO DESPACHO 7.4 NOTIFICADO NA RPI NO 2449, DE 12/12/2017 |
    2018-04-03| B09A| Decision: intention to grant|
    2018-05-22| B16A| Patent or certificate of addition of invention granted|
    优先权:
    申请号 | 申请日 | 专利标题
    US201161443218P| true| 2011-02-15|2011-02-15|
    US61/443,218|2011-02-15|
    US201161521134P| true| 2011-08-08|2011-08-08|
    US61/521,134|2011-08-08|
    PCT/US2012/024222|WO2012112350A2|2011-02-15|2012-02-08|Dental compositions comprising ethylenically unsaturated addition-fragmentation agent|
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