Cationically polymerizable adhesive composition containing an acidic component and methods and materials employing same

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) an epoxide;
• (b) an acidic component comprising one or more compounds having at least one acidic or acidogenic functional group and a reactive olefinic moiety;
• and
• (c) a photoinitiator capable of initiating cationic polymerization, wherein said adhesive composition is able to bond to hard tissue.

A method of bonding to a material, comprising:

• (a) providing a material selected from the group consisting of hard tissue, dental metals, ceramics, and composite restoratives;
• (b) applying to said material an adhesive composition comprising a mixture of a cationically polymerizable component, an acidic component comprising one or more compounds having at least one acidic or acidogenic functional group, and an initiator capable of initiating cationic polymerization;
• and
• (c) exposing said adhesive composition to polymerization conditions to form a hardened composition adhered to said material.

A method of bonding to hard tissue, comprising:

• (a) applying an acidic component to said hard tissue to form a first layer;
• (b) subsequently applying a cationically polymerizable component, an acidic component comprising one or more compounds having at least one acidic or acidogenic functional group and cationic initiator mixture to said hard tissue to form a second layer;
• and
• (c) exposing said first and second layer to polymerization conditions to form a hardened coposition adhered to said hard tissue.

An adhesive composition for bonding to hard tissue, comprising:

• (a) a cationically polymerizable component;
• (b) an acidic component;
• and
• (c) an initiator capable of initiating cationic polymerization,
• wherein said adhesive composition is able to bond to hard tissue, and wherein said acidic component is selected from the group consisting of
• maleic anhydride;
• ring-opened derivatives of maleic anhydride having at least one acid or acidogenic functionality of structure (2), (3) or (4):
• wherein each R1, R2, R3, and R4 is independently selected from any aliphatic or aromatic radical;
• polymeric polycarboxylic acids of the formula:
• wherein each R is independently selected from H, CH3, or CH2CO2H, and n is any integer and copolymers that include said polycarboxylic acids so long as said polymeric polycarboxylic acid is at least partially soluble in the other components of the adhesive composition;
• a compound of the formula:
• wherein at least two of R1, R2, and R3 are independently selected from any aliphatic or aromatic radical that has at least one polymerizable group and wherein the resulting compound does not interfere with cationic polymerization;
• a compound of the formula:
• wherein R4 is any aliphatic or aromatic radical that has at least two polymerizable groups and wherein the resulting compound does not interfere with cationic polymerization;
• a compound of the formula:
• wherein R is an alkyl group having 2 to 4 carbons or a cycloalkyl group having 5 to 6 carbons, each M is independently selected from hydrogen, metal ions, complex organic cations, and alkyl groups, and each n is an integer independently selected from 1 to 4;
• and
• combinations thereof.

An adhesive composition for bonding to hard tissue, comprising:

• (a) a cationically polymerizable component;
• (b) an acidic component comprising a polycarboxylic acid having a number average molecular weight that is less than about 10,000;
• and
• (c) an initiator capable of initiating cationic polymerization, wherein said adhesive composition is able to bond to hard tissue.

An adhesive composition for bonding to hard tissue, comprising:

• (a) a cationically polymerizable component;
• (b) an acidic component selected from the group consisting of maleic acid;
• maleic anhydride;
• 2-(methacryloyloxy)ethyl maleate;
• the reaction products of maleic anhydride and 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate (HEMA), 2- and 3-hydroxypropylacrylate and methacrylate, 1,3- and 2,3-dihydroxypropylacrylate and methacrylate, 2-hydroxypropyl-1,3-diacrylate and dimethacrylate, 3-hydroxypropyl-1,2diacrylate and dimethylacrylate, pentaerythritol diacrylate and dimethacrylate, 2-aminoethylacrylate, 2-aminoethylmethacrylate, 2- and 3-aminopropylacrylate and methacrylate, 1,3- and 2,3-diaminopropylacrylate and methacrylate, 2-aminopropyl-1,3-diacrylate and dimethacrylate, 3-aminopropyl-1,2diacrylate and dimethylacrylate;
• homopolymers and copolymers of poly(acrylic acid), polymethacrylic acid, and poly(itaconic acid);
• 2-({N-[2-(2-methylprop-2-enoyloxy)ethyl]carbamoyloxy}methyl)-3-[N-(2-prop-2-enoyloxyethyl)carbamoyloxy]propanoic acid (PDMA);
• ethylenediamine tetraacetic acid (EDTA);
• and mono-, di-, and tri- salts of EDTA;
• and
• (c) an initiator capable of initiating cationic polymerization, wherein said adhesive somposition is able to bond to hard tissue.

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) a cationically polymerizable component;
• (b) an acidic component;
• and
• (c) an initiator capable of initiating cationic polymerization,
• wherein said adhesive composition is able to bond to hard tissue with a bond strength of at least about 10 kg/cm2, and
• wherein said acidic component is selected from the group consisting of
• maleic anhydride;
• ring-opened derivatives of maleic anhydride having at least one acid or acidogenic functionality of structure (2), (3) or (4):
• wherein each R1, R2, R3, and R4 is independently selected from any aliphatic or aromatic radical;
• polymeric polycarboxylic acids of the formula:
• wherein each R is independently selected from H, CH3, or CH2CO2H, and n is any integer and copolymers that include said polycarboxylic acids so long as said polymeric polycarboxylic acid is at least partially soluble in the other components of the adhesive composition;
• a compound of the formula:
• wherein at least two of R1, R2, and R3 are independently selected from any aliphatic or aromatic radical that has at least one polyrnerizable group and wherein the resulting compound does not interfere with cationic polymerization;
• a compound of the formula:
• wherein R4 is any aliphatic or aromatic radical that has at least two polymerizable groups and wherein the resulting compound does not interfere with cationic polymerization;
• a compound of the formula:
• wherein R is an alkyl group having 2 to 4 carbons or a cycloalkyl group having 5 to 6 carbons, each M is independently selected from hydrogen, metal ions, complex organic cations, and alkyl groups, and each n is an integer independently selected from 1 to 4;
• and
• combinations thereof.

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) acationically polymerizable component present in an amountof about 10-99% by weight of the total weight of the mixture;
• (b) an acidic component present in an amount of about 0.1-30% by weight of the total weight of the mixture and comprising maleic anhydride or one or more of ring-opened derivatives of maleic anhydride having at least one acid or acidogenic functionality of structure (2), (3) or (4):
• wherein each R1, R2, R3 and R4 is independently selected from any aliphatic or aromatic radical;
• and
• (c) an initiator capable of initiating cationic polymerization and present in an amount of about 0.1-10% by weight of the total weight of the mixture, wherein said adhesive composition is able to bond to hard tissue with a bond strength of at least about 10 kg/cm2.

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) a cationically polymerizable component present in an amount of about 10-99% by weight of the total weight of the mixture;
• (b) an acidic component present in an amount of about 0.1-30% by weight of the total weight of the mixture and comprising polymeric polycarboxylic acids of the formula:
• wherein each R is independently selected from H, CH3, or CH2CO2H, and n is any integer and copolymers that include said polycarboxylic acids so long as said polymeric polycarboxylic acid is at least partially soluble in the other components of the adhesive composition;
• and
• (c) an initiator capable of initiating cationic polymerization and present in an amount of about 0.1-10% by weight of the total weight of the mixture, wherein said adhesive composition is able to bond to hard tissue with a bond strength of at least about 10 kg/cm2.

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) a cationically polymerizable component present in an amount of about 10-99% by weight of the total weight of the mixture;
• (b) an acidic component present in an amount of about 0.1-30% by weight of the total weight of the mixture and comprising a compound of the formula:
• wherein at least two of R1, R2, and R3 are independently selected from any aliphatic or aromatic radical that has at least one polymerizable group and wherein the resulting compound does not interfere with cationic polymerization;
• and
• (c) an initiator capable of initiating cationic polymerization and present in an amount of about 0.1-10% by weight of the total weight of the mixture, wherein said adhesive composition is able to bond to hard tissue with a bond strength of at least about 10 kg/cm2.

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) a cationical ly polymerizable component present in an amount of about 10-99% by weight of the total weight of the mixture;
• (b) an acidic component present in an amount of about 0.1-30% by weight of the total weight of the mixture and comprising a compound of the formula:
• wherein R4 is any aliphatic or aromatic radical that has at least two polymerizable groups and wherein the resulting compound does not interfere with cationic polymerization;
• and
• (c) an initiator capable of initiating cationic polymerization and present in an amount of about 0.1-10% by weight of the total weight of the mixture, wherein said adhesive composition is able to bond to hard tissue with a bond strength of at least about 10 kg/cm2.

An adhesive composition for bonding to hard tissue, comprising a mixture of:

• (a) a cationically polymerizable component present in an amount of about 10-99% by weight of the total weight of the mixture;
• (b) an acidic component present in an amount of about 0.1-30% by weight of the total weight of the mixture and comprising a compound of the formula:
• wherein R is an alkyl group having 2 to 4 carbons or a cycloalkyl group having 5 to 6 carbons, each M is independently selected from hydrogen, metal ions, complex organic cations, and alkyl groups, and each n is an integer independently selected from 1 to 4;
• and
• (c) an initiator capable of initiating cationic polymerization and present in an amount of about 0.1-10% by weight of the total weight of the mixture, wherein said adhesive composition is able to bond to hard tissue with a bond strength of at least about 10 kg/cm2.