Germ-repellent Silicone Rubber and Preparation Method and Application thereof

Abstract

The present invention provides a germ-repellent silicone rubber comprising: a silicone rubber substrate and a germ-repellent active ingredient incorporated therein; wherein, the silicone rubber substrate includes polydimethylsiloxane; the germ-repellent active ingredients include poly(ethylene oxide) and silicone oil or their derivatives. The disclosed germ-repellent silicone rubber reduces the bacterial growth by inhibiting their adherence to the surface instead of killing them, does not contribute to super bacteria formation nor cause skin irritation.

Claims

1. A germ-repellent silicone rubber comprising: a silicone rubber substrate and germ-repellent active ingredients incorporated therein; wherein the mass ratio of the silicone rubber substrate to the germ-repellent active ingredient is 100:(2-10); the silicone rubber substrate includes component A and component B, component A includes polydimethylsiloxane with vinyl groups; component B includes polydimethylsiloxane with functional groups; the germ-repellent active ingredients include a polyethoxylated non-ionic surfactant, wherein the polyethoxylated non-ionic surfactant is selected from a combination of polyethylene glycol or the derivative thereof with silicone oil.

2. The germ-repellent silicone rubber according to claim 1, wherein the mass ratio of the silicone rubber substrate to the germ-repellent active ingredient is 100:(2-3).

3. The germ-repellent silicone rubber according to claim 1, wherein the mass ratio of component A to component B is (0.5-1.5):(0.5-1.5).

4. The germ-repellent silicone rubber according to claim 1, wherein the mass ratio between polyethylene glycol or the derivative thereof and silicone oil is (60-40):(40-60).

5. The germ-repellent silicone rubber according to claim 1, wherein said polyethylene glycol or the derivative thereof comprises PEG 200, PEG 400, mPEG 600, and poly(ethylene glycol) sorbitol hexaoleate.

6. The use of the germ-repellent silicone rubber of claim 1 in pacifier, teether, milk bottle, facial cleaning head and mouthpiece.

7. The use of the germ-repellent silicone rubber of claim 2 in pacifier, teether, milk bottle, facial cleaning head and mouthpiece.

8. The use of the germ-repellent silicone rubber of claim 3 in pacifier, teether, milk bottle, facial cleaning head and mouthpiece.

9. The use of the germ-repellent silicone rubber of claim 4 in pacifier, teether, milk bottle, facial cleaning head and mouthpiece.

10. The use of the germ-repellent silicone rubber of claim 5 in pacifier, teether, milk bottle, facial cleaning head and mouthpiece.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG. 1A shows the schematic illustration of the bacteria-killing mechanism.

[0023] FIG. 1B shows the schematic illustration of the germ-repellent mechanism.

[0024] FIG. 2 shows the procedure of swab testing of the germ-repellent silicone rubber with referring to ISO 22196 industrial standard.

[0025] FIG. 3 shows the industrial manufacturing process for LSR products.

[0026] FIG. 4 shows the transparency of the three samples before and after the treatment.

[0027] FIG. 5 shows the transparency of samples treated with Bi-component GR modifier and single-component modifier before and after treatment.

[0028] FIG. 6 shows the durability test results.

[0029] FIG. 7 shows the mechanical properties of germ-repellent silicone.

DETAILED DESCRIPTION OF INVENTION

[0030] The present invention is not to be limited in scope by any of the following descriptions. The following examples or embodiments are presented for exemplification only.

[0031] References in the specification to “one embodiment”, “an embodiment”, “an example embodiment”, etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment may not necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described.

[0032] Values expressed in a range format should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of “about 0.1% to about 5%” should be interpreted to include not only the explicitly recited concentration of about 0.1 wt. % to about 5 wt. %, but also the individual concentrations (e.g., 1%, 2%, 3%, and 4%) and the sub-ranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, and 3.3% to 4.4%) within the indicated range.

[0033] In this document, the terms “a” or “an” are used to include one or more than one and the term “or” is used to refer to a nonexclusive “or” unless otherwise indicated. In addition, it is to be understood that the phraseology or terminology employed herein, and not otherwise defined, is for the purpose of description only and not of limitation. Furthermore, all publications, patents, and patent documents referred to in this document are incorporated by reference herein in their entirety, as though individually incorporated by reference. In the event of inconsistent usages between this document and those documents so incorporated by reference, the usage in the incorporated reference should be considered supplementary to that of this document; for irreconcilable inconsistencies, the usage in this document controls.

[0034] In the methods of preparation described herein, the steps can be carried out in any order without departing from the principles of the invention, except when a temporal or operational sequence is explicitly recited. Recitation in a claim to the effect that first a step is performed, and then several other steps are subsequently performed, shall be taken to mean that the first step is performed before any of the other steps, but the other steps can be performed in any suitable sequence, unless a sequence is further recited within the other steps. For example, claim elements that recite “Step A, Step B, Step C, Step D, and Step E” shall be construed to mean step A is carried out first, step E is carried out last, and steps B, C, and D can be carried out in any sequence between steps A and E, and that the sequence still falls within the literal scope of the claimed process. A given step or sub-set of steps can also be repeated.

[0035] Furthermore, specified steps can be carried out concurrently unless explicit claim language recites that they be carried out separately. For example, a claimed step of doing X and a claimed step of doing Y can be conducted simultaneously within a single operation, and the resulting process will fall within the literal scope of the claimed process.

Definitions

[0036] The singular forms “a,”, “an” and “the” can include plural referents unless the context clearly dictates otherwise.

[0037] The term “about” can allow for a degree of variability in a value or range, for example, within 10%, or within 5% of a stated value or of a stated limit of a range.

[0038] The term “phr” defines as the per hundred rubber, which refers to the compound ingredients given as parts per 100 unit mass of the rubber polymer, which is prevalently referred as the polymeric base resin.

DESCRIPTION

[0039] The following examples accompanied with drawings will illustrate the present invention in more detail.

[0040] FIGS. 1A-1B show a major advantage of the germ-repellent technology of the present invention over the conventional bacteria-killing approach relying on the use of antibiotics or silver ion-based bactericidal formulations. The conventional biocides or silver-based antimicrobial agents would promote the development of drug-resistant super bacteria and/or have cytotoxic effect to human. The built-in germ-repellent technology of the present invention reduces bacterial growth by inhibiting their adherence to the surface instead of killing them, does not contribute to super bacteria formation nor cause skin irritation. What's more, the service life of germ-repellent products is longer and more cost effective.

Examples

Germ-Repellent Silicone

[0041] Silicone is one of the most versatile thermoset polymers for medical and food-grade applications due to its highly inert chemistry and strong silicon-oxygen bonding. Herein, platinum-cured silicone rubber (Silopren LSR2060 (Momentive)) will be studied as follows.

[0042] To impart germ-repellent properties into the silicone rubber, different modifiers were incorporated into the base materials (LSR). The effective modifiers can be polyethylene glycol (PEG), polypropylene glycol (PPG), PEG or PPG terminated, or copolymers with side chains of PEG or PPG groups, as indicated in Table 1.

TABLE-US-00001 TABLE 1 Material list for additives to be used for modifying silicone Name Brand Chemical Formula HLB Number ENEA-0260 Allyloxy(polyethylene)oxide Gelest [00001] 5-8 silicone polyether copolymer Gelest [00002] SIA0479.0 O-allyloxy(polyetheneoxy) trimethylsilane Gelest [00003] N/A OFX-0193 silicone polyether copolymer Dow Corning [00004] 12.2 PEG 200 Polyethylene glycol, Mw.200 Kermel_Tianjing [00005] 9.1 PEG 400 Polyethylene glycol, Mw.400 Kermel_Tianjing [00006] 12.9-13.1 mPEG 600 Methyl polyethylene glycol, Mw.600 Chenrun_Nantong [00007] 19.5 TWEEN ® 80 Polyoxyethylenesorbitan monooleate Sigma Remark 1 15 Remark 1: [00008]

Preparation of Germ-Repellent Silicone

[0043] The germ-repellent silicone (LSR) sample could be prepared by separately weighing Part A (polydimethylsiloxane with vinyl groups) and Part B (polydimethylsiloxane with functional groups) of LSR system into a clean plastic cup. Then specific amounts of modifier in phr are added into the same cup. As an example, in the preparation of germ-repellent silicone rubber(LSR2060/2 phr (PEG 200+silicone oil)), 50 g of Part A, 50 g of Part B and 2 g of (PEG 200+silicone oil) were weighed into a clean cup. Wherein the mass ratio between PEG and silicone oil is 1:1. A high-speed mixer operating at 2000 rpm for 5 mins was used for the mixing. The mixing could also be accomplished in a liquid injection molding (LIM) machine, where the LSR and the liquid modifier could be fed into and mixed in the injection screw as a single mixing step. After mixing, the curing processes of different grades of LSR are shown in Table 2. The sheets were cut into desired 4 cm×4 cm plastic sheet for germ-repellence evaluation or die-cut into sample specimens according to the relevant ASTM standard for mechanical properties determination.

TABLE-US-00002 TABLE 2 Curing condition for silicone rubbers LSR grade Processing Shin-Etsu KE-2090 120° C. × 10 mins + 150° C. × 1 Hr (self-bonding, medical grade) Wacker LR 3038 165° C. × 5 mins + 200° C. × 4 Hrs (food-contact grade) Shin-Etsu CHN 2003 120° C. × 10 mins (No post cure grade)

Germ-Repellent Efficacy of Modified LSR2060

[0044] Test specimen will be made into a 5×5 cm sheet with 0.5-2 mm thickness. The present invention referred to the industrial testing standard ISO 22196 to characterize the germ-repellent efficacy. FIG. 2 shows the detailed procedure for germ-repellent test, which is also called as swab test. This test can be carried out by experiment and accredited third parties (e.g. SGS).

[0045] Experiments of the present invention confirmed the feasibility of developing a GR-SR formulation with 99% reduction of bacterial growth by adding poly (ethylene glycol) or its derivatives with silicone oil into the silicone rubber substrate. The specific GR efficacy testings are shown in table 3 and table 4.

[0046] It can be seen from table 3 that the germ-repellent silicone rubber of the present invention has strong GR efficacy. It can be seen from table 4 that the Bi-component GR modifier has a better effect than the single-component modifier.

TABLE-US-00003 TABLE 3 GR efficacy testing GR efficacy testing results (2 phr modifier) LSR Grade E. coli S.A. Shin-Etsu KE-2090 −97.9% −98.4% ( self-bonding, medical grade) Wacker LR 3038 −96.4% −98.4% (food-contact grade) Shin-Etsu CHN 2003 −99.4% −96.7% (No post cure grade)

TABLE-US-00004 TABLE 4 GR efficacy comparison (LSR base resins:Shin-Etsu KE-2090) GR efficacy test LSR Grade GR-SR formulations E.coli S.A. Remarks Shin-Etsu OFX-0193 −91.1% −76.1% x KE-2090 (silicone polyether copolymer GR modifier) GR-SR −99.5% −98.2% ✓ (Bi-component GR modifier)

Transparency Comparison

[0047] The transparency comparison results are shown in table 5. The transparency of the three samples before and after the treatment is shown in FIG. 4. The transparency of samples treated with Bi-component GR modifier and single-component modifier before and after treatment is shown in FIG. 5.

[0048] It can be seen from table 5 and FIG. 4 that the germ-repellent silicone rubber of the present invention has good transparency. It can be seen from FIG. 5 that the Bi-component GR modifier has a better effect on transparency than the single-component modifier.

TABLE-US-00005 TABLE 5 GR-SR transparency Shin-Etsu Wacker Shin-Etsu KE-2090 LR 3038 CHN-2003 (2 phr) (2 phr) (2 phr) Reduced Light −6.2% −3.6% −3.6% Transmittance (GR-SR vs control)

GR Efficacy—Durability

[0049] The durability test results are shown in FIG. 6. It can be seen from FIG. 6 that after been washed 270 times, the sample can still maintain high efficacy.

Mechanical Properties of Germ-Repellent Silicone

[0050] The property of Tensile strength is determined for the selected GR-modified SR(FIG. 7). It can be seen from FIG. 7 that all 3 GR-SR samples mechanical strength reduction<5% versus unmodified control according to ASTM D 412.

Application

[0051] In the final stage of the project, we will integrate our germ-repellent SR formulation into sponsor's existing manufacturing process in plant. The current production process is thermoset injection molding (FIG. 3). The mold shapes can be chosen for pacifier, teether, bottle, facial cleaning head or mouth piece according to sponsor's requirements.

Material Safety Assessment

[0052] These as—prepared GR-SR prototypes are intended for baby and personal care applications. The add-on germ-repellent agents selected are generally recognized as safe (GRAS) agents. To evaluate their material safety, the GR-SR prototypes will be tested according to industrial standards such as FDA21 CFR 177.2600, EU food contact AP2004-5, REACH etc., specifically for products intended for contact with food, 9 migration tests evaluate the overall or specific migration after extracted in solvents (e.g. water, n-hexane, acetic acid, etc.). Material food contact testing will be conducted at accredited external laboratories according to industrial standards, such as US FDA CFR 21 Part 177.2600 titled “rubber articles intended for repeated use”. It sets the extraction limit for water (aqueous food) and n-hexane (fatty foods) at a reflux condition for 7 hours, as 20 mg/in.sup.2 and 175 mg/in.sup.2 respectively. A succeeding 2 hours extraction under the same condition should contain extractable within the limit of 1 and 4 mg/in.sup.2 respectively. The EU food contact AP2004-5 is for silicone rubber overall migration (water, 3% acetic acid, 10% ethanol, substitute of rectified olive oil) will be conducted at externally as well. The test results of the samples in this application are all passed.