Cross-linked plastic material with an intrinsic antimicrobial effect based on unsaturated polyesters

Abstract

The present invention relates to a radically curable chemical composition in the form of a resin for the production of materials with an intrinsically antimicrobial effect, as well as a process for the production of such resins and materials, as well as the use of an amino-functionalized styrene derivative as reactive diluents. The cross-linked plastic formed upon curing has an intrinsically antimicrobial effect without the use of additional biocides.

Claims

1. An unsaturated polyester resin composition for the production of products with antimicrobial effect containing a) an unsaturated polyester from dicarboxylic acid and/or anhydride on the one hand, and diol with a molar ratio of 1.25:1 to 0.75:1 on the other hand, with dicarboxylic acid and/or the anhydride having been at least partially functionalized with a radically reactive double bond, and b) styrene derivative as reactive diluent, with 0.5 to 8 styrene derivative molecules being present in the composition for each double bond in component a), and with at least one entity having been amino-functionalized from styrene derivative, dicarboxylic acid and/or diol selectively, with the formula for the amino-functionality being, irrespective of the entity,
—(CH.sub.2).sub.q—NH.sub.pR.sup.1R.sup.2A.sub.p with q being either 0, 1 or 2, with q≠0, provided the functionality is bound to an aromatic, p being 0 or 1, R.sup.1 having been selected from H, linear or branched or cyclic alkyl residues with 1 to 10 carbon atoms, R.sup.2 being a linear or branched or cyclic alkyl residue with 1 to 10 carbon atoms, A being the anion of an acid, and the amine nitrogen N of the above formula being neutral (p=0) or positively (p=1) charged.

2. Composition according to claim 1, characterised in that the styrene derivative has been amino-functionalized.

3. Composition according to claim 2, characterised in that the amino-functionalized styrene derivative is one of these substances, ##STR00005## with R.sup.1 being a hydrogen, and R.sup.2 having been selected from the group of isopropyl, tert-butyl, tert-pentyl.

4. The composition according to claim 1, characterised in that it contains at least 20% w/w of a mixture of components a) and b).

5. The composition according to claim 1, with 1.5 to 4 styrene derivative molecules being contained in the composition for each double bond in component a).

6. A method of coating, varnishing, casting, dipping, laminating, gap impregnation, spinning, gluing, resin injection, pressing, injection moulding, pultrusion, filling or winding, said method comprising curing the composition of claim 1.

7. Process for the production of cured products, with a composition according to claim 1 being cured.

8. Product with antimicrobial effect containing a cured composition according to claim 7.

9. The product according to claim 8 selected from the following products: furniture and furniture surfaces, adhesives, veneer and paper laminates, buttons, handles, switches and housings, plates, floorings, tubes, profiles, tanks and containers for drinking water, food and oil, casing, roof coverings, light panels, sealants, putty, rawplug filler, polymer concrete, agglo marmor, kitchen sinks, shower basins, bath tubs, wash basins, toilet seats, garden furniture, garden fences, facade plates, cellar window shafts, vehicle parts, lighting support, wind turbines, impregnations, binding agents, casting compounds, filler, and/or reaction mortar, coatings, varnishes, gel coats, top coats, ships, boats or leisure equipment.

10. Process for the production of amino-functionalized styrene derivative, whereas a) in a first step an aqueous alkali hydroxide solution with a concentration between 3 and 7 mol/1 is provided, b) in a second step an half molar equivalent to one molar equivalent amount of amine with at least one hydrogen atom bound to a nitrogen atom is added to the aqueous alkali hydroxide solution, c) in a third step 0.2 to 0.5 molar equivalent of halogen alkyl styrene in relation to the amount of alkali hydroxide is added, d) in a fourth step the resulting reaction solution is stirred after adding all of the halogen alkyl styrene, over a period of 2 to 48 hours, and e) in a fifth step the resulting amino-functionalized styrene derivative is separated from the remaining reaction solution.

11. The composition according to claim 1 where the styrene derivative is selected from ##STR00006## with R.sup.1 and/or R.sup.2 having been independently selected from the group methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, 3-pentyl, iso-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, whereas R.sup.1 can also be H.

12. The composition according to claim 1, characterised in that it contains at least 80% w/w of a mixture of components a) and b).

13. The composition according to claim 2, characterised in that the amino-functionalized styrene derivative has 10 to 20 carbon atoms.

14. The composition according to claim 2, characterised in that the amino-functionalized styrene derivative has 12 to 18 carbon atoms.

15. The composition according to claim 2, wherein that the amino-functionalized styrene derivative is selected from the group consisting of N-(4-ethenylbenzyl)-2-methylpropane-2-amine, tert-butyl-amino-methyl styrene, N-(4-ethenylbenzyl) ethanamine, ethyl-aminomethyl-styrene, N-(4-ethenylbenzyl)propane-1-amine, n-propyl-aminomethyl-styrene, N-(4-ethenylbenzyl)propane-2-amine, isopropyl-aminomethyl styrene, N-(4-ethenylbenzyl)butane-1-amine, n-butyl-aminomethyl-styrene, N-(4-ethenylbenzyl)butane-2-amine, sec-butyl-aminomethyl styrene, N-(4-ethenylbenzyl)-2-methylpropane-1-amine, isobutyl-aminomethyl-styrene, N-(4-ethenylbenzyl)pentane-1-amine, n-pentyl-aminomethyl-styrene, N-(4-ethenylbenzyl)-3-methylbutane-1-amine, isopentyl-aminomethyl-styrene, N-(4-ethenylbenzyl)pentane-3-amine, 3-pentyl-aminomethyl-styrene, N-(4-ethenylbenzyl)-2-methylbutane-2-amine, tert-pentyl-aminomethyl-styrene, N-(4-ethenylbenzyl)cyclopentanamine, cyclopentyl-aminomethyl-styrene, N-(4-ethenylbenzyl)cyclohexanamine, cyclohexyl-aminomethyl-styrene, N-(4-ethenylbenzyl)-N,N-dimethylamine, dimethyl-aminomethyl-styrene, N-(4-ethenylbenzyl)-N,N-diethylamine, diethyl-aminomethyl-styrene, N-(4-ethenylbenzyl)-N-(propane-2-yl)propane-2-amine, diisopropyl-aminomethyl-styrene and mixtures thereof.

Description

WORKING EXAMPLES

Production of Amino-Functionalized Styrene Derivative (General Provision)

(1) In a 1,000 ml flask, 200 ml of water and 42 g (1.05 mol) of NaOH were added and after complete dissolution, 1.05 mol of the respective amine was added. The flask was heated to a temperature of 60-85° C. while stirring, and over the space of approximately 75 minutes, a solution containing 53.42 g (0.35 mol) of chloromethyl styrene and 150 ml of THF was added dropwise. After completion of the dropwise addition, the reaction flask was left in the oil bath up to a total reaction time of 4-120 hours, stirring continuously, with the reaction time and reaction temperature depending on the amine used. Analysis was carried out using GC-MS. Purification was carried out by means of vacuum distillation.

(2) According to this general provision, amine-functionalized styrene derivative were synthesized using the following amines: tert-butylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, n-pentylamine, 3-penylamine, isopentylamine, tert-butylamine, cyclopentylamine, cyclohexylamine, diethylamine, diisopropylamine.

(3) The tert-butyl-amino-methyl styrene received with tert-butylamine was abbreviated TBAMS. It was produced at a reaction temperature of 70° C. and a post-stirring time of 24 hours and a conversion rate of >98% and >98% selectivity. Under vacuum distillation, the boiling point of TBAMS was 115° C. at 6 mbar.

Example 1

(4) Condensation of UP 1 (FS.sub.1,0 DEG.sub.0,5 NPG.sub.0,5)

(5) For the production of polyester, 719.63 g of fumaric acid, 329.24 g of diethylene glycol and 322.92 g of neopentyl glycol were weighed into a 2 l four necked flask on a condensation apparatus, and after adding 100 ppm of hydroquinone and 220 ml of water, it was heated up to 80° C. while constantly stirring and under a continuous nitrogen stream (5 l/h). Subsequently, the reaction temperature was increased at a heating rate of approximately 10 K/10 min to 210° C. During constant water separation, the reaction temperature was kept at 210° C. for 2.5 hours. Then, the polyester was cooled down to 115° C. and filled into brown glass bottles.

(6) The acid number established through titration was 28 mg KOH/g UP. The melting viscosity determined with ICI cone plate viscometer was 780 mPas (150° C., 10000 s.sup.−1).

1A. Resin Production and Curing (2.5 Mol TBAMS Per Mol UP 1 Double Bond)

(7) For the production of the resin, the unsaturated polyester (56.2 g; 28.1 (% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (143.8 g; 71.9% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(8) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

(9) The share of polyester corresponds to that of component a) and is 56.2 g (28.1% w/w).

(10) The constitutive repeating unit of the polyester is as follows:

(11) ##STR00004##

(12) The molar mass of the repeating unit is 370.35 g/mol and contains 2 reactive fumaric acid double bonds.

(13) This results in n.sub.Dop=f.Math.m.sub.Dop/M.sub.Dop=2.Math.56.2 g/370.35 g/mol=0.303 mol

(14) The styrene derivative proportion (tert-butyl-amino-methyl styrene, TBAMS) corresponds to component b) and is 143.8 g (71.9% w/w). The molar mass is 189.3 g/mol.

(15) This results in n.sub.Sty=m.sub.Sty/M.sub.Sty=143.8 g/189.3 g/mol=0.760 mol

(16) The ratio of styrene derivative compared with double bonds is:
n.sub.Sty: n.sub.Dop=0.760 mol:0.303 mol=2.51:1

1B. Resin Production and Curing (2.25 Mol TBAMS Per Mol UP 1 Double Bond)

(17) For the production of the resin, the unsaturated polyester (45.5 g; 30.3% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (104.6 g; 69.7% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(18) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

(19) In this working example, the ratio of styrene derivative compared with double bonds in component a) is 2.25:1.

1C. Resin Production and Curing (2.0 Mol TBAMS Per Mol UP 1 Double Bond)

(20) For the production of the resin, the unsaturated polyester (46.1 g; 32.9% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (93.9 g; 67.1% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(21) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

(22) In this working example, the ratio of styrene derivative compared with double bonds in component a) is 2.00:1.

Example 2

(23) Condensation of UP 2 (FS.sub.0,5 THPS.sub.0,5 NPG.sub.1,0)

(24) For the production of polyester, 348.21 g of fumaric acid, 456.45 g of tetrahydrophthalic acid anhydride and 643.65 g of neopentyl glycol were weighed into a 2 l four necked flask on a condensation apparatus, and after adding 200 ppm of hydroquinone, 400 ppm of Fascat 4100 (n-butylstannoic acid) and 170 g of water, it was heated up to 140° C. while constantly stirring and under a continuous nitrogen stream (5 l/h). Subsequently, the reaction temperature was increased at a heating rate of approximately 10 K/30 min to 200° C. During constant water separation, the reaction temperature was maintained for 4 hours, then it was increased to 210° C. and maintained for another 2 hours. After cooling down to 120° C., the polyester was filled into brown glass bottles.

(25) The acid number established through titration was 29.8 mg KOH/g UP. The melting viscosity determined with ICI cone plate viscometer was 770 mPas (150° C., 10000 s.sup.−1).

2A. Resin Production and Curing (2.5 Mol TBAMS Per Mol UP 2 Double Bond)

(26) For the production of the resin, the unsaturated polyester UP 2 (47.1% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (52.9% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(27) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

2B. Resin Production and Curing (2.25 Mol TBAMS Per Mol UP 2 Double Bond)

(28) For the production of the resin, the unsaturated polyester UP 2 (49.8% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (50.2% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(29) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

2C. Resin Production and Curing (2.0 Mol TBAMS Per Mol UP 2 Double Bond)

(30) For the production of the resin, the unsaturated polyester UP 2 (52.7% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (47.3% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(31) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

Example 3

(32) Condensation of UP-3 (MSA.sub.1,0 DEG.sub.0,5 NPG.sub.0,5)

(33) For the production of polyester, 637.40 g of maleic acid anhydride, 345.18 g of diethylene glycol and 338.54 g of neopentyl glycol were weighed into a 2 l four necked flask on a condensation apparatus, and after adding 100 ppm of hydroquinone, it was heated up to 80° C. while constantly stirring and under a continuous nitrogen stream (5 l/h). Subsequently, the reaction temperature was increased at a heating rate of approximately 10 K/10 min to 200° C. During constant water separation, the reaction temperature was maintained for 3 hours. Then, the polyester was cooled to 115° C. by switching off the heating and it was filled into brown glass bottles.

(34) The acid number established through titration was 29.4 mg KOH/g UP. The melting viscosity determined with ICI cone plate viscometer was 220 mPas (150° C., 10000 s.sup.−1).

3A. Resin Production and Curing (2.5 Mol TBAMS Per Mol UP 3 Double Bond)

(35) For the production of the resin, the unsaturated polyester UP 3 (28.1% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (71.9 w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(36) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

3B. Resin Production and Curing (2.0 Mol TBAMS Per Mol UP 3 Double Bond)

(37) For the production of the resin, the unsaturated polyester UP 3 (32.9% w/w) and the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) (67.1% w/w) were placed on a wagon carriage for 14 days for dissolution and, once they had been fully dissolved, were azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(38) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

Example 4

(39) Amino-Functionalizing of UP 3 (MSA.sub.1,0 DEG.sub.0,5 NPG.sub.0,5)

(40) 237.10° g of the unsaturated polyester UP 3 was filled into a 11 flask with reflux condenser and heated to 65° C. While stirring, 11.7 g (corresponds to 12.5 mol % of fumaric and maleic ester units of UP 3) tert-butylamine was added dropwise over a period of 20 minutes, then the temperature was increased step by step to 140° C., and maintained for one hour. Then, the unsaturated polyester was cooled down to 115° C. and filled into brown glass bottles.

(41) Resin Production and Curing

(42) For resin production, 50% w/w of the functionalized, unsaturated polyester UP 3 and 50% w/w of the amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) were filled into a brown glass bottle and placed onto a wagon carriage for dissolution for 14 days. Once it had been fully dissolved, the resin was azo-initiated with 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako. Subsequently, around 8 g each of the transparent, homogeneous resin were placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(43) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

Example 5

(44) Condensation of UP 5 (FS.sub.1,0 DEG.sub.3,306 NPG.sub.0,51 TBBHEA.sub.0,204)

(45) For the production of polyester, 928.56 g of fumaric acid, 259.73 g of diethylene glycol, 424.93 g of neopentyl glycol, 263.14 g of tert-butyl-bis hydroxy-ethylamine (TBBHEA) and 100 g of water were weighed into a 2 l four necked flask on a condensation apparatus, and after adding 200 ppm of hydroquinone, it was heated up to 140° C. while constantly stirring and under a continuous nitrogen stream (20 l/h) over a period of 2 hours, and maintained at 140° C. for 55 minutes under incipient water separation. Subsequently, the reaction temperature was increased at a heating rate of approximately 15 K/10 min to 170° C., kept at 170° C. for approximately 30 minutes and then cooled down to room temperature. On the following day, the reaction mixture was heated uniformly to 185° C. over a period of approximately 210 minutes. Subsequently, the temperature was increased to 190° C. over a period of 20 minutes, and maintained at 190° C. for 90 minutes under further water separation. Then, the polyester was cooled to 115° C. by switching off the heating and it was filled into brown glass bottles.

(46) The acid number established through titration was 34.7 mg KOH/g UP. The melting viscosity determined with ICI cone plate viscometer was 920 mPas (150° C., 1.250 s.sup.−1).

(47) Resin Production and Curing

(48) For resin production, 51.72 g (40% w/w) of UP 5, 77.58 g (60% w/w) of amino-functionalized reactive diluent TBAMS (tert-butyl-amino-methyl styrene) and 200 ml of acetone were filled into a single neck flask and stirred until the unsaturated polyester had fully dissolved. Subsequently, the acetone was separated in a vacuum using a rotary evaporator. Once the acetone had been separated, 2% w/w of azo initiator V601 [dimethyl 2,2′-azobis(2-methylpropionate)] by Wako was added. After homogenisation of the resin-initiator-mixture, around 8 g each of the mixture was placed on various glass Petri-dishes and cured under nitrogen atmosphere at 70° C. for 2 hours, at 80° C. for 2 hours and at 90° C. for 2 hours.

(49) The resulting, fully cured UP thermoset was tack-free and hard. The UP thermoset was practically odourless and showed excellent antimicrobial characteristics.

(50) Procedure for the Determination of Dynamic-Mechanical Behaviour and Glass Transition Temperature

(51) To determine the network-T.sub.G, glass fibre-reinforced thermoset test pieces were produced from the resin described in examples 10, 2A, 2C, 3B and 4, and characterized by dynamic mechanical analysis (DMA).

(52) The DMA 242 by Netzsch, which was used here, allows the determination of the storage modulus and the loss modulus, as well as the loss factor of a sample as a function of time and temperature by subjecting it to a sinusidal oscillating force.

(53) The resins produced in the working examples with 2% w/w of initiator (V601 by Wako) were used for the production of the required test pieces.

(54) For this purpose, three 15×15 cm layers of Saertex® glass fibre fabrics (biaxial 0°/90°/type: S14EB540-00620-T1300-487000) impregnated with the respective resin were placed into a 150×150×5 mm sheet form lined with a screwable Mylar® film and freed from air bubbles by pressing down with a spatula. Subsequently, the cavity of the form was fully filled with more resin, covered with Mylar® film and closed by screwing on the top platen. The product was cured in a drying oven for 2 hours at 70, for 2 hours at 80 and for 2 hours at 90° C.

(55) After cooling, the GRP plates were cut using a table circular saw and sanded down to the correct test piece size with a belt if necessary.

(56) Parameters and measurements for the DMA analyses carried out:

(57) Measurements of the test pieces: 50×10×5 mm

(58) Deformation mode: Dual cantilever

(59) Amplitude 30 μm

(60) Dynamic force: 7.55 N

(61) Static force: 4 N

(62) Temperature range: 20-160° C.

(63) Heating rate: 2 K/min

(64) Frequency: 1 Hz/10 Hz

(65) Atmosphere: N.sub.2

(66) Flow rate N.sub.2: 5 ml/min

(67) Procedure for Antimicrobial Tests

(68) The method applied is based on the Japanese standard JIS Z 2801:2000. The testing microorganism used in the test was the pathogen staphylococcus aureus. A standard pathogen (ATCC 6538), not a multiresistant one, was used.

(69) For each test microbe (here: staphylococcus aureus), a germ count specific for the microorganism was set under the conditions used for the production of the initial solution or initial suspension. For staphylococcus aureus, the germ count was 108 per ml (see further explanations below).

(70) Antimicrobial activity was determined by comparing the growth of staphylococcus aureus on reference surfaces with that on the specimen materials.

(71) The reference material were empty Petri-dishes. The specimens consisted of Petri-dishes, on which a thin layer of polymer had been poured. For each test series, three reference plates were used for the determination of the initial germ count (separate test from the test on antimicrobial behaviour) and three reference plates and three specimen plates were used for the determination of the surface germ count after incubation.

(72) All plates were seeded with 400 μl of staphylococcus aureus seeding suspension set to a germ count of 4.0-10*10.sup.5 CFU/ml.

(73) The seeding suspension was covered with a sterile PP film to prevent evaporation. Directly following seeding, the three specimen plates and three reference plates were placed into an incubation cabinet and kept there for 2 and 24 hours, respectively, at 35° C. and 90% humidity.

(74) For the determination of the germ count in the seeding solution (initial germ count), three reference plates each were washed out directly after seeding by adding 10 ml SCDLP bouillon medium (soybean casein digest broth with lecithin and polysorbate) to the Petri-dish. The film was turned using a pair of sterile pincers and flooded several times using a 1 ml pipette. The Petri-dish was swirled in a figure-eight motion before 1 ml of the rinsing solution was pipetted in the first dilution step. After preparing the first serial dilution, the germ count was determined using the Drop Plate method. In a dual approach, on a Plate Count (PC) Agar plate, 5 drops of 10 μl each were pipetted into the sector of the respective dilution step using the Drop Plate method. The plates were incubated for 2 hours and 24 hours respectively at 37° C.

(75) Rinsing and determination of germ count on the reference and the specimen plates after incubation was carried out using the same method as the determination of the initial germ count. In addition to raising the detection limit for the sample plates, the germ count of the immediate rinsing solution was determined using the pour plate technique. Again, using a dual approach, 1 ml of the solution each was placed in an empty Petri-dish, and liquid, 45° C. warm, PC agar was poured onto it. By swirling the dish in a figure eight motion, the bacteria were distributed in the agar. The plates were incubated for 48 hours at 37° C.

(76) Following incubation, the colonies in the Petri-dish were counted. The assumption was that each bacteria had grown a visible colony. After incubation, the colonies were visible with the naked eye—a transilluminator could be used to improve visibility.

(77) Based on the volume of the seeding solution and the dilution ratio employed, conclusions could be drawn regarding the living germ count per volume unit (i.e. per ml) of seeding solution. The calculation was based on the weighted arithmetic mean using the following formula:

(78) $c=\frac{.Math.c}{n_1.Math.1+n_2.Math.0.1}.Math.d$
where c represents the weighted arithmetic mean Σ.sub.c represents the total of colonies of all Petri-dishes or sectors included in the calculation n.sub.1 represents the number of Petri-dishes or sectors in the lowest dilution step n.sub.2 represents the number of Petri-dishes or sectors in the next higher dilution step d represents the factor of lowest evaluated dilution step

(79) Using the pour plate technique, Petri-dishes with up to 300 CFU (colony forming units) could be counted. Only plates of up to 150 CFUs per sector could be evaluated using the Drop Plate method.

(80) When determining the germ count per ml, the dilution factor F1 had to be taken into consideration. These led to the total of the volume of SCDLP bouillon and the volume of bacterial suspension on the seeded plate, divided by the volume of bacterial suspension on this seeded plate.

(81) $F_1=\frac{10\mathrm{ml}+0.4\mathrm{ml}}{0.4\mathrm{ml}}=26$
F.sub.1 Dilution factor of SCDLP bouillon

(82) The following formula resulted for the total germ count on the seeded specimen plates and reference plates, respectively, using the Pour plate technique

(83) $\mathrm{CFU}=\frac{.Math.c}{n_1.Math.1+n_2.Math.0.1}.Math.d.Math.F_1$

(84) Another dilution factor was relevant for the Drop Plate method, because a quarter of a plate was only seeded with 50 μl, i.e. 0.05 ml. To deduct the germ count per ml from this, 0.05 ml had to be converted to 1 ml, by multiplying by 20.
F.sub.2=26.Math.20
F.sub.2 Dilution factor to calculate CFU per ml using the Drop Plate method.

(85) The total germ count of the seeded specimen plates and reference plates was calculated taking into consideration all dilution factors according to the following formula:

(86) $\mathrm{CFU}=\frac{.Math.c}{n_1.Math.1+n_2.Math.0.1}.Math.d.Math.F_2$

(87) For the calculation of antimicrobial activity, in each test series, the individual results for the germ count per plate were summarized as a simple arithmetic mean as a basis for calculating the log.sub.10 reduction factor between sample plate and reference plate.

(88) The calculation was made using the following formula:
log.sub.10−reduction=log.sub.10 (kg).sub.Ref(x)−log.sub.10 (kg).sub.Pr(x)
with
(kg).sub.Ref(x) CFU on the reference plates at the time x and
(kg).sub.Pr(x) CFU on the specimen plates at the time x.

(89) According to JIS Z 2801:2000, antimicrobial activity takes place in a log reduction of at least 0.2 after an incubation period of 24 hours.

(90) In those cases where on the agar plates holding the specimens with the lowest dilution step in the pour plate technique no colonies could be counted, the result was shown as <10 CFU/ml according to the test standard provisions.

Results of the Dynamic Mechanical and the Antimicrobial Tests

(91) TABLE-US-00001 Mass T.sub.G T.sub.G Initial germ Reference germ fraction of at at count (log count after 2 h (log Example Composition UP TBAMS 1 HZ 10 HZ CFU/ml) CFU/ml) 1A FS.sub.1,0DEG.sub.0,5NPG.sub.0,5 0.72 — — 5.7 5.5 1B FS.sub.1,0DEG.sub.0,5NPG.sub.0,5 0.70 — — 5.7 5.5 1C FS.sub.1,0DEG.sub.0,5NPG.sub.0,5 0.67 132.4 142.6 5.7 5.5 2A FS.sub.0,5THPSA.sub.0,5NPG.sub.1,0 0.53  98.1 106.7 5.3 — 2B FS.sub.0,5THPSA.sub.0,5NPG.sub.1,0 0.50 — — 5.3 — 2C FS.sub.0,5THPSA.sub.0,5NPG.sub.1,0 0.47  95.8 103.3 5.3 — 3A MSA.sub.1,0DEG.sub.0,5NPG.sub.0,5 0.72 — — 5.6 — 3B MSA.sub.1,0DEG.sub.0,5NPG.sub.0,5 0.67 110.7 118.6 5.7 — 4 MSA.sub.1,0DEG.sub.0,5NPG.sub.0,5 + TBA 0.50 119.7 128.4 5.7 — 5 FS.sub.1,0DEG.sub.0,3NPG.sub.0,5TBBHEA.sub.0,2 0.60 119.3 128.9 5.7 — Germ count on Log Reference germ Log reduction Log specimen surface reduction count after 24 h (log after 24 h (log reduction Example after 2 h (log CFU/ml) after 2 h CFU/ml) CFU/ml) after 24 h 1A 3.3 2.2 — — — 1B 3.6 1.9 — — — 1C 3.0 2.5 — — — 2A — — 8.2 1.0 7.2 2B — — 8.2 1.0 7.2 2C — — 8.2 1.0 7.2 3A — — 7.5 1.0 6.5 3B — — 7.8 1.0 6.8 4 — — 7.8 1.0 6.8 5 — — 7.8 1.0 6.8 Notes: 1. All products showed a marked antimicrobial effectiveness. 2. For some specimens, such as 2A, 2B, 2C, the values for log reduction after 24 hours were identical. This is owed to the fact that the three measurements were carried out in parallel, so that the same reference germ count was used. As the residual germ count of the specimens after 24 hours was always below the method's detection limit, according to the standard it was indicated as log 1, which resulted in identical values for log reduction.