Adhesive having a long processing time and stable viscosity
11591500 · 2023-02-28
Assignee
Inventors
Cpc classification
C09J4/06
CHEMISTRY; METALLURGY
C08K5/0025
CHEMISTRY; METALLURGY
C09J4/06
CHEMISTRY; METALLURGY
A61C13/10
HUMAN NECESSITIES
International classification
A61C13/10
HUMAN NECESSITIES
C09J4/06
CHEMISTRY; METALLURGY
Abstract
A polymerizable adhesive composition containing an olefinically functionalized carbohydrate, a polymerizable liquid monomer, and optionally at least one polymerization initiator or initiator system is described. The adhesive composition is particularly well suited for adhering plastic components as well as is preferably provided with sufficiently long processing time for adhering artificial teeth on denture bases. The viscosity of the adhesive composition may be adjusted to the respected processing conditions.
Claims
1. Polymerizable dental hot- and/or polymerisable adhesive composition containing at least one carbohydrate comprising (i) at least one polymerizable liquid monomer, which comprises (ii) at least one polymerization initiator and/or initiator system for polymerization, containing 1. An initiator for hot- or auto-polymerization comprising a peroxide and/or azo compound, and optionally an aromatic tertiary amine as polymerization accelerator, or 2. A redox system comprising a) a peroxide, diketone and amine or b) (i) barbituric acid or thiobarbituric acid or a barbituric acid derivative or thiobarbituric acid derivative and (ii) at least one copper salt or copper complex and (iii) at least one compound having an ionic halogen atom, and optionally 3. A photoinitiator comprising a-hydroxyketone, azo compound or acylphosphineoxide, and (iii) at least one polymerizable olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixtures thereof, wherein the composition has a viscosity of 50 to 5000 mPa.Math.s.
2. Adhesive composition according to claim 1, wherein (iii) is an olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative, or mixtures thereof, soluble in (i).
3. Adhesive composition according to claim 1, wherein the composition comprises two components A and B, (i) component A being present as paste and comprising (a1) at least one polymerizable liquid monomer, (a2) at least one olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixtures thereof, soluble in (a1), and component B being present as paste and comprising (b1) at least one polymerizable liquid monomer, (b2) at least one olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixtures thereof, soluble in (i), (b1), or (ii) component A being present as paste and comprising (a1) at least one powdered olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixtures thereof, and component B being present as liquid or paste and comprising (b1) at least one polymerizable liquid monomer, and (b2) optionally at least one powdered olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixtures thereof, soluble in (ii), (a1), and the respective component (A) and/or (B) contains in (i) and (ii) at least one polymerization initiator or an initiator system for radical polymerization, and/or for photo-polymerization.
4. Adhesive composition according to claim 1, wherein the polymerizable liquid monomer comprises a) at least one acrylate, acrylic acid alkyl ester, alkyl 2-acrylic acid alkyl ester, aryl 2-acrylic acid alkyl ester, aryl alkyl 2-acrylic acid alkyl ester, each independently having 1 to 20 C-atoms in the alkyl group, each independently having 6 to 14 C-atoms in the aryl group, each independently having 6 to 14 C-atoms in the aryl alkyl group and each independently having 1 to 10 C-atoms in the alkyl ester group, or a mixture comprising at least two of the said monomers, and/or b) N-alkyl- or N-alkenyl-substituted acryloyloxy carbamate having a molecular mass of less than or equal to 250 g/mol, difunctional urethane (meth)acrylate, multifunctional urethane (meth)acrylate oligomer or also dendrimer, and/or c) di-, tri-, tetra- or multi-functional monomer, not being urethane (meth)acrylate, or a mixture comprising at least two of the said monomers.
5. Adhesive composition according to claim 1, wherein the polymerizable liquid monomer comprises at least one acrylate selected from acrylate, methyl (meth)acrylate (MMA), methacrylic acid ethyl ester (EMA), and ethyl acrylic acid ethyl ester.
6. Adhesive composition according to claim 1, wherein the polymerizable olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixture thereof comprises at least one olefinically functionalized di- and polysaccharide, olefinically functionalized di- and polysaccharide derivative, olefinically functionalized cellulose, olefinically functionalized cellulose derivative, olefinically functionalized starch, olefinically functionalized starch derivative, olefinically functionalized chitin and/or olefinically functionalized chitin derivative.
7. Adhesive composition according to claim 1, wherein the polymerizable olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixture thereof comprises an olefinically functionalized cellulose, cellulose derivative or a mixture thereof.
8. Adhesive composition according to claim 1, wherein the polymerizable olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixture thereof comprises alkenyl group, alkenyl aryl group, unsaturated acyl group, acryloyl group, acryl group, acrylamide group, 2-alkyl acryl group, 2-alkyl acryloyl group, wherein the alkyl group comprises 1 to 10 C-atoms, 2-alkyl acrylamide group, wherein the alkyl group comprises 1 to 10 C-atoms, as at least one olefinic group, or at least one acryl group, 2-alkene acryl group, alkenyl group, alkenyl aryl group, unsaturated acryl group, bridged over at least one bifunctional heteroatom selected from O—, N—, and S— atoms.
9. Adhesive composition according to claim 1, wherein the olefinically functionalized carbohydrate or olefinically functionalized carbohydrate derivative comprises olefinically functionalized cellulose acetate butyrate, (acryloyloxy alkyl) cellulose acetate butyrate, (acrylamido alkyl) cellulose acetate butyrate, each independently having 1 to 10 C-atoms in the bifunctional alkyl group.
10. Adhesive composition according to claim 1, wherein the olefinically functionalized carbohydrate or olefinically functionalized carbohydrate derivative is selected from (acrylamido methyl) cellulose acetate butyrate or (acrylamido ethyl) cellulose acetate butyrate.
11. Adhesive composition according to claim 1, wherein the olefinically functionalized carbohydrate or olefinically functionalized carbohydrate derivative has a number average molecular weight distribution of Mn 1,000 to 50,000 g/mol, each determined by means of GPC.
12. Adhesive composition according to claim 1, wherein the adhesive composition is a dental hot- or auto-polymerizable adhesive composition, comprising (i) 60 to 78% by weight at least one polymerizable liquid monomer, (ii) 0 to 5% by weight at least one polymerization initiator, and (iii) 22 to 40% by weight at least one polymerizable olefinically functionalized carbohydrate, olefinically functionalized carbohydrate derivative or mixture thereof, wherein the total composition equates to 100% by weight.
13. Adhesive composition according to claim 1, wherein the composition has a viscosity of 50 to 600 mPa.Math.s, or a high viscosity of 1500 to 2000 mPa.Math.s, depending on the application.
14. Adhesive composition according to claim 1, wherein the composition is an auto-polymerizable 2-component adhesive composition.
15. Kit comprising a 2-component adhesive composition according to claim 3, comprising A) at least one polymerizable liquid monomer component, B) at least one olefinically functionalized carbohydrate or olefinically functionalized carbohydrate derivative or mixture thereof, wherein the adhesive composition contains in component (A) and/or (B) (i) at least one polymerization initiator and optionally a polymerization accelerator or an initiator system for auto-polymerization.
16. Method for adhering artificial teeth in respectively one cavity for receiving of at least parts of an artificial tooth in a dental denture base, comprising the steps of: a) using a higher viscous hot- or auto-polymerizable adhesive composition (2) for positioning and orientation of respectively one artificial tooth in a cavity for receiving an artificial tooth, and b) using a lower viscous photo-polymerizable adhesive composition (1) for filling the marginal gap formed between the tooth and the cavity margin, by, in step a) (i) inserting the hot- or auto-polymerizable adhesive composition according to claim 1 in the respective cavity is made, (ii) providing the basal side of the respective artificial tooth with the hot- or auto-polymerizable adhesive composition, and inserting the respective tooth with the basal side into the respective cavity of the dental denture base, and optionally positioning and orientating the tooth in the respective cavity, and b) (i) optionally filling the marginal gap formed between the cavity margin of the respective cavity and the respective tooth inserted with a photo-polymerizable adhesive composition.
17. Method of using the adhesive composition according to claim 1, said method comprising adhering said adhesive composition to plastics, filled plastics, mineral substrates, metallic substrates, dental plastics, dental filled plastics, dental mineral substrates and/or dental metallic substrates, dental, medical or surgical prosthetic parts, technical components, electronic components, of automotive components, or computer components.
18. Method of using the kit according to claim 15, said method comprising adhering the 2-component adhesive composition to plastics, filled plastics, mineral substrates, metallic substrates, dental plastics, dental filled plastics, dental mineral substrates and/or dental metallic substrates, dental, medical or surgical prosthetic parts, technical components, electronic components, of automotive components, or computer components.
Description
EXEMPLARY EMBODIMENTS AND MEASURING METHODS
(1) Viscosity
(2) TABLE-US-00001 Measuring device: Measuring system: Rheometer: Anton Paar - Physica Plate/Plate Measuring system Measuring plate MCR 301 PP50 Rotation time experiment: Measurinq profile: (presettings) Measuring gap = 0.2 mm Shear rate d(gamma)dt = 10 1/s constant Measuring temperature = 20° C. Timing = 20 measuring points Measuring point duration = 2 seconds Waiting time until experiment is started = 1 minute
(3) Analysis:
(4) Creating a mean value graph from single measurements; calculation type=arithmetic average; 2. averaging of all data points of the mean value graph; calculation of the viscosity in [mPa.Math.s] at 20° C.
(5) Adhesion or cohesion was determined according to DIN 13998 (2012) using a Zwick 2010 apparatus, wherein, deviating from the standard, pure cohesion fracture was sought. The adhesive composition comprising the powder or the olefinically functionalized carbohydrate or derivative, respectively, contains as polymerization initiator and polymerization accelerator Speedcure BEDB (2-n-Butoxyethyl-4-(dimethylamino)benzoate) and Perkadox L-DFG (Di-Benzoyl peroxide). The fracture toughness was determined using a Zwick 2010 machine referring to DIN 13998.
(6) TABLE-US-00002 TABLE 1 Comparison of the fracture toughness of adhesion as well as of the processing times Shear bond strength Mix- processing Fracture ture Powder Liquid time [h] toughness F.sub.max [N] 1 Jaylink 103M.sup.[*.sup.] EMA 24 h 449 cohesive (polymerizable fracture cellulose) 2 Jaylink 103M MMA — 192 partially (polymerizable cohesive cellulose) fracture 3 PMMA M.sub.w 332 MMA 9 min 319 cohesive fracture 4 Cellulose Ethocel EMA — 115 adhesive std. 45 Premium fracture (non polymerizable cellulose) 5 PMMA M.sub.w 332: MMA 15 min 294 cohesive Jaylink fracture 103M (7:1) 6 Wieland dental MMA 6-10 min 209 partially CAD CAM bond cohesive fracture .sup.[*]Jaylink 103M M.sub.n approx. 10,000 g/mol
(7) From the results in Table 1 it can be seen that good fracture strengths may be achieved with the mixtures of olefinically functionalized cellulose and methylmethacrylate or ethylmethacrylate. In addition, with the adhesive composition in the combination ethylmethacrylate with olefinically functionalized cellulose, on the one hand, the processing time could be quite significantly extended to 24 hours and, at the same time, the fracture toughness could be increased to F.sub.max=449 [N] resulting in a pure cohesive break.
(8) TABLE-US-00003 TABLE 2 Estimation of the processing time in hours [h] of the first mixture in Table 1 by viscosity measurements Period after production of the mixture 0 h 0.5 h 1.5 h 3.5 h 24 h Viscosity 448.7 452.3 455.4 441.3 Gelation (mPa .Math. s)
(9) A mixture of 1 to 14 g cellulose to EMA in weight ratio 1:3.2 was produced, which is classified as medium viscous (450 mPa.Math.s). The viscosity of 14 g of the mixture was determined immediately after addition of the initiator and the accelerator Perkadox L-DFG and Speedcure BEDB at 20° C. using viscosimeter Anton Paar Physica MCR301 rheometer from a shear rate of 10 (1/s) on.
(10) The preceding measurement results merely show negligible change of the viscosity within the first 3.5 hours. In further experiments, initiator was added to 2.3 g of mixture 1 visually confirming this result. The adhesive was still applicable after 24 h.
(11) A pre-mixture comprising olefinically functionalized cellulose to EMA in weight ratio of 1:3,2 having a content of 2% by weight amine(s) was stored for one month at 27° C. and change of the viscosity was determined, see Table 3. No change was observed over a period of 8 weeks.
(12) TABLE-US-00004 TABLE 3 Viscosity measurements in hours [h] and weeks [w] Period after production of the mixture 0 h 1 w 2 w 4 w 8 w Viscosity (mPa .Math. s) 586.2 576.2 562.3 569 Visually no change.
BRIEF DESCRIPTION OF THE DRAWINGS
(13)
(14)
(15)
(16)
(17)