Compositions which undergo light-induced cationic curing and their use

• US 6,084,004 A
• Filed: 08/21/1998
• Issued: 07/04/2000
• Est. Priority Date: 08/21/1997
• Status: Expired due to Term

• Current Assignee: 3M Deutschland GmbH (3M Company)
• Original Assignee: ESPE Dental AG (3M Company)
• Inventors: Eckhardt, Gunther, Weinmann, Wolfgang
• Primary Examiner(s): Seidleck, James J.
• Assistant Examiner(s): McClendon, Sanza L.
• Application Number:
  US09/138,281
• Time in Patent Office: 683 Days
• Field of Search: 522/25, 522/7, 522/168, 522/100, 522/170, 522/31
• US Class Current: 522/25
• CPC Class Codes: A61K 6/20 Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• CPC Class Codes: A61K 6/30 Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• CPC Class Codes: A61K 6/891 Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08G 59/68 characterised by the catalysts used
• CPC Class Codes: C08G 65/18 Oxetanes
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: G03F 7/038 Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021

Abstract

The invention relates to compositions which undergo cationic curing with visible light, comprising:

(a) 0.01 to 8 wt. % of at least one diaryliodonium compound,

(b) 0.01 to 8 wt. % of at least one α-dicarbonyl compound,

(c) 10.0 to 99.9 wt. % of at least one compound containing epoxide groups and/or oxetane groups,

(d) 0 to 85 wt. % of modifiers, such as fillers, dyestuffs, pigments, flow improvers, thixotropic agents, polymeric thickeners, additives having an oxidizing action, stabilizers and retardants, characterized in that they additionally comprise

(e) 0.001 to 5 wt. % of at least one aromatic amine.

The compositions have a low intrinsic color, cure with little smell and, after curing, give compositions with very good mechanical properties.

Claims

1. Composition which undergoes cationic curing with visible light, comprising

(a) 0.01 to 8 wt. % of at least one diaryliodonium compound,

(b) 0.01 to 8 wt. % of at least one α

-dicarbonyl compound,

(c) 10.0 to 99.9 wt. % of at least one compound containing epoxide groups and/or oxetane groups,

(d) 0 to 85 wt. % of modifiers, such as fillers, dyestuffs, pigments, flow improvers, thixotropic agents, polymeric thickeners, additives having an oxidizing action, stabilizers and retardants,

characterized in that it additionally comprises

(e) 0.001 to 5 wt. % of at least one aromatic amine.

2. Composition according to claim 1, characterized in that it comprises the constituents

(a) in an amount of 0.1 to 5 wt. %

(b) in an amount of 0.1 to 5 wt. % and

(e) in an amount of 0.01 to 3 wt. %.

3. Compositions according to claim 1, characterized in that the diaryliodonium compounds of constituent (a) have the following structure:

space="preserve" listing-type="equation">[((R.sup.1).sub.a Ar.sup.1)--I--(Ar.sup.2 (R.sup.2).sub.b)].sup.+ Y.sup.-

wherein the symbols denote;

Ar¹, Ar² independently of one another different, substituted or unsubstituted, fused or non-fused aromatic systems having 4 to 20 C atoms, preferably phenyl, tolyl, cumyl, anisyl, chlorophenyl, nitrophenyl, naphthyl, thienyl, furanyl and pyrazolyl,

R¹, R² independently of one another an H atom, an aliphatic radical having 1 to 19, preferably 1 to 9 C atoms, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C═

O)--, F, Cl, Br, SiR³₃ and/or NR³₂, wherein R³ is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═

O and/or --O(C═

O)--, wherein the aromatics Ar¹ and Ar² can be bonded to one another via R¹ and/or R²,

a and b independently of one another an integer from 1 to 5 and

Y^- an anion of little nucleophilicity of the formula

space="preserve" listing-type="equation">K.sub.x L.sub.y

wherein the symbols denote;

K an element of main group III, V or VII, preferably B, Al, P, Sb, As or I

x a number from 1 to 4

L independently of one another aromatic, aliphatic, araliphatic or cycloaliphatic radicals having 1-25 C atoms, in which one or more C atoms can be replaced by F, Cl, Br or I, and

y a number from 0 to 6.

4. Composition according to claim 3, characterized in that Y^- is PF₆^-, SbF₆^- or B(C₅ F₅)₄.

5. Composition according to claims 1, characterized in that the α

-dicarbonyl compounds of constituent (b) have the following structure;

##STR4## in which R⁴ and R⁵ independently of one another can be substituted or unsubstituted and aliphatic or aromatic and R⁴ and R⁵ together can form ring structures which are unsubstituted or substituted by aliphatic, cycloaliphatic, aromatic, heteroaromatic or fused aromatic radicals.

6. Composition according to claim 5, characterized in that it comprises, as constituent (b), camphorquinone, benzil, 2,3-butanedione and/or 3,3,6,6-tetramethylcyclohexanedione, preferably camphorquinone.

7. Composition according to claim 1, characterized in that the aromatic amines of constituent (e) have the following structure:

##STR5## in which R⁶, R⁷ and R⁸ independently of one another denote an H atom, an aliphatic, aromatic or araliphatic radical having 1 to 19, preferably 1 to 7 C atoms, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C═

O)--, SiR⁹₃ and/or NR⁹₂, and R⁹ is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═

O and/or O(C═

O), and z can assume numerical values from 1 to 5 and R⁶ and R⁷ or/and R⁶ and R⁸ together can form ring structures which can be unsubstituted or substituted by aliphatic, cycloaliphatic, aromatic, heteroaromatic or fused aromatic radicals.

8. Composition according to claim 7, characterized in that it comprises, as constituent (c), dimethylaniline, diethylaniline, ethyl 4-dimethyl-aminobenzoate, 2-butoxyethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminobenzaldehyde, benzaldoximes, azomethines, benzylideneaniline, hydrobenzamide, benzoins, benzils, hydrobenzoins and/or benzoic acid benzyl esters, preferably ethyl 4-dimethyl-aminobenzoate, 2-butoxyethyl 4-dimethylaminobenzoate or 2-ethylhexyl 4-dimethylaminobenzoate.

9. Composition according to claim 1, characterized in that the compounds of constituent (c) containing epoxide groups and/or oxetane groups have the following structure:

##STR6## wherein the symbols denote;

R¹⁰ an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C═

O)--, SiR₃ and/or NR₂, and wherein R is an aliphatic radical having 1 to 7 C atoms, it being possible for one or more C atoms to be replaced by O, C═

O and/or --O(C═

O)--,

R¹¹ an aliphatic, cycloaliphatic or aromatic radical having 1 to 18, preferably 1 to 15 C atoms or a combination of these radicals, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C═

O)--, SiR₃ and/or NR₂, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═

O and/or --O(C═

O)--,

R¹², R¹³, R¹⁴, R¹⁵ independently of one another an H atom or an aliphatic radical having 1 to 9, preferably 1 to 7 C atoms, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C═

O)--, SiR₃ and/or NR₂, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═

O and/or --O(C═

O)--,

n 2 to 7,

m 1 to 10,

p 1 to 5,

q 1 to 5.

10. Composition according to claim 9, characterized in that it comprises, as component (c), 1,3,5,7-tetrakis-(2,1-ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxane, 1,10-decanediylbis(oxymethylene)bis(3-ethyloxetane), 1,3,5,7,9-pentakis(2,1-ethanediyl-3,4-epoxycyclohexyl) -1,3,5,7,9-pentamethylcyclopentasiloxane, Vinylcyclohexene oxide, vinylcyclohexene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, bis(2,3-epoxycyclopentyl)ether, 3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4epoxycyclohexyl-5,5-spiro-3,4-epoxy(cyclohexanemetadioxane), 1,4-butanediyl-bis(oxymethylene)-bis-(3-ethyloxetane), 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,1,3,3-tetramethyl-1,3-bis(2,1-ethanediyl-3,4-epoxycyclohexyl)disiloxane and/or bis-(3,4-epoxycyclohexylmethyl) adipate.

11. Composition according to claim 1, characterized in that it comprises, as the additives of constituent (d) having an oxidizing action, cumene hydroperoxide, di-tert-butyl peroxide, diaryl peroxides, dibenzoyl peroxide, tert-butyl perbenzoate, tert-butyl isononanoate, potassium persulphate and/or sodium perborate.

12. Composition according to claim 1, characterized in that it comprises, as fillers of constituent (d), quartz, ground, optionally X-ray-opaque or reactive glasses, splinter polymers, sparingly soluble fluorides, silica gels and/or pyrogenic silicic acid or granules thereof.

13. The composition according to claim 1, wherein the composition is not cured by means of free radicals.

16. The composition according to claim 9, wherein n is 2 to 5, m is 1 to 7, p is 1 to 4 and q is 1 to 4.

17. The composition according to claim 9, wherein n is 2 to 4, m is 1 to 5, p is 1 or 2 and q is 1 or 2.

18. The composition according to claim 12, wherein the sparingly soluble fluorides are CaF₂ or YF₃.

19. The method of gluing, embedding or coating a substrate, comprising contacting a substrate with the composition of claim 1.

20. A dental filling material comprising the composition according to claim 1.

21. A bonding material comprising the composition of claim 1.

22. A filling cement comprising the composition according to claim 1.

23. A fixing cement comprising the composition of claim 1.

24. A plastic for a prostheses comprising the composition according to claim 1.

25. A veneer material comprising the composition according to claim 1.

26. A sealing material comprising the composition according to claim 1.

27. Artificial teeth comprising the composition according to claim 1.

14. Composition which undergoes cationic curing with visible light, comprising

(a) 0.01 to 8 wt. % of at least one diaryliodonium compound having the following structure:

space="preserve" listing-type="equation">[(R.sup.1).sub.a Ar.sup.1)--I--(Ar.sup.2 (R.sup.2).sub.b)].sup.+ Y.sup.-

wherein the symbols denote;

Ar¹ , Ar² independently of one another different, substituted or unsubstituted, fused or non-fused aromatic systems having 4 to 20 C atoms, preferably phenyl, tolyl, cumyl, anisyl, chlorophenyl, nitrophenyl, naphthyl, thienyl, furanyl and pyrazolyl,

R¹, R² independently of one another an H atom, an aliphatic radical having 1 to 19, preferably 1 to 9 C atoms, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C=0)--, F, Cl, Br, SiR³₃ and/or NR³₂, wherein R³ is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═

O and/or --O(C═

O)--, wherein the aromatics Ar¹ and Ar² can be bonded to one another via R¹ and/or R²,

a and b independently of one another an integer from 1 to 5 and Y^- =B(C₆ F₅)₄^-,

(b) 0.01 to 8 wt. % of at least one α

-dicarbonyl compound,

(c) 10.0 to 99.9 wt. % of at least one compound containing epoxide groups and/or oxetane groups,

(d) 0 to 85 wt. % of modifiers, such as fillers, dyestuffs, pigments, flow improvers, thixotropic agents, polymeric thickeners, additives having an oxidizing action, stabilizers and retardants,

characterized in that it additionally comprises

(e) 0.001 to 5 wt. % of at least one aromatic amine having the following structure;

##STR7## in which R⁶, R⁷ and R⁸ independently of one another denote an H atom, an aliphatic, aromatic or araliphatic radical having 1 to 19 C atoms, it being possible for one or more C atoms to be replaced by O, C═

O, --O(C═

O)--, SiR⁹₃ and/or NR⁹₂, and R⁹ is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═

O and/or O(C═

O), and z can assume numerical values from 1 to 5 and R⁶ and R⁷ and/or R⁶ and R⁸ together can form ring structures which can be unsubstituted or substituted by aliphatic cycloaliphatic, aromatic, heteroaromatic or fused aromatic radicals.

15. The composition according to claim 14, wherein R⁶, R⁷ and R⁸ independently of one another denote H atom, an aliphatic, aromatic or araliphatic radical having 1 to 7 C atoms.