CN104725864A - Antibacterial silicone rubber and preparation method thereof - Google Patents

Antibacterial silicone rubber and preparation method thereof Download PDF

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Publication number
CN104725864A
CN104725864A CN201510165646.XA CN201510165646A CN104725864A CN 104725864 A CN104725864 A CN 104725864A CN 201510165646 A CN201510165646 A CN 201510165646A CN 104725864 A CN104725864 A CN 104725864A
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CN
China
Prior art keywords
carboxylic acid
silicon rubber
acid
silver
antimicrobial
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CN201510165646.XA
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Chinese (zh)
Inventor
周海燕
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Hangzhou Ge Fang Novel Material Science And Technology Ltd
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Hangzhou Ge Fang Novel Material Science And Technology Ltd
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Priority to CN201510165646.XA priority Critical patent/CN104725864A/en
Publication of CN104725864A publication Critical patent/CN104725864A/en
Pending legal-status Critical Current

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Abstract

The invention relates to silicone rubber and a preparation method thereof, in particular to antibacterial silicone rubber and a preparation method thereof. The antibacterial silicone rubber comprises, by weight percentage, 96.5-98% of silicone rubber, 0.1-10% of antibacterial additive containing silver ions and 0.1-5% of carboxylic acid, wherein the antibacterial additive containing silver ions comprises one or more of silver-loaded zirconium phosphate, silver carboxylates, silver-impregnated zeolite, glass particles with silver-loaded surface coatings, colloidal silver particles or nano silver particles; the carboxylic acid comprises one or more of single acid, double acid, tribasic acid, fatty acid, alicyclic acid, alicyclic acid aromatic carboxylic acid or the anhydride of the carboxylic acid. The silicone rubber is efficient in antibacterial activity and applicable to various application requiring antibacterial performance.

Description

A kind of antimicrobial silicon rubber and preparation method thereof
Technical field
The present invention relates to a kind of silicon rubber and preparation method thereof, particularly relate to a kind of antimicrobial silicon rubber and preparation method thereof.
Background technology
Silver-containing antibacterial additive has application in multiple synthesized polymer material, but majority all not effectively or with silicone rubber crosslinking system interferes with each other in silicon rubber.This low usefulness may be because the concentration of the active silver ion being diffused into silastic surface is not high enough.Increase these and have its practical significance and application demand containing the activity of silver additive in silicon rubber.
Summary of the invention
The object of this invention is to provide a kind of antimicrobial silicon rubber and preparation method thereof, to solve problems of the prior art, silicon rubber of the present invention has outstanding germ resistance.
Antimicrobial silicon rubber of the present invention, comprises by weight percentage:
Silicon rubber 96.5-98%
The antimicrobial additive 0.1-10% of silver ion
Carboxylic acid 0.1-5%
Further, comprise by weight percentage:
Silicon rubber 96.5-98%
The antimicrobial additive 0.2-5% of silver ion
Carboxylic acid 0.2-3%
Further, comprise by weight percentage:
Silicon rubber 96.5-98%
The antimicrobial additive 0.5-2% of silver ion
Carboxylic acid 0.5-2%
Further, described silicon rubber comprises high viscosity silicon rubber and liquid silastic.
Further, the glass particle that the antimicrobial additive of described silver ion comprises silver-loaded zirconium phosphate, silver carboxylate, silver-impregnated zeolite, top coat carry silver, colloidal metal Argent grain or nano metal Argent grain one or more.
Further, described carboxylic acid comprises one or more of acid anhydrides of single acid, bisgallic acid, triprotic acid, lipid acid, alicyclic acid, alicyclic acid aromatic carboxylic acid or above-mentioned carboxylic acid.
Further, when described carboxylic acid is saturated fatty acid, the amount of carbon atom of described carboxylic acid is no more than 14; When described carboxylic acid has a unsaturated double-bond, the amount of carbon atom of described carboxylic acid is no more than 20.When amount of carbon atom arrives certain value, carboxylic acid is that thick being not easy to mixes enforcement, and simultaneously along with the increase of amount of carbon atom, the acidity of carboxylic acid can reduce, and also can destroy the surface component of silicon rubber.
Prepare the method for antimicrobial silicon rubber, comprise the following steps:
A) component A of liquid silastic, the antimicrobial additive of silver ion and carboxylic acid are mixed by corresponding weight percent;
B) add platinum catalyst, at room temperature stir 30-90min;
C) sulfidization molding is mixed with the B component of liquid silastic.
Or
A) antimicrobial additive of high viscosity silicon rubber, silver ion and carboxylic acid are mixed in mixing roll by corresponding weight percent;
B) platinum catalyst is added, at room temperature mixing 30-90min;
C) sulfidization molding.
Antimicrobial silicon rubber of the present invention comprises silicon rubber, the additive of silver ion and carboxylic acid, wherein, the additive of silver ion and the content of carboxylic acid only account for a small amount of weight percent, do not affect the normal use of silicon rubber, silicon rubber after crosslinked is tested in containing the aqueous solution of microorganism, shows efficient anti-microbial activity.Wherein carboxylic acid this in this concentration range, do not show germ resistance, and the additive of silver ion activity is also very low at such low concentrations can not reach industry requirement.Reason is as follows, carboxylic acid it can improve the solubleness of Ag-containing compound and the rate of diffusion in silicon rubber, cause silver ions in the raising of rubber surface concentration, can make originally do not have the very low silicon rubber of germ resistance or germ resistance to embody efficient anti-microbial activity.Wherein, these antiseptic-germicides can be various forms: such as argent, colloid or nano-Ag particles, the compound of silver and complex compound etc.
This antimicrobial silicon rubber may be used in the antibacterial application of various needs, and such as, medical treatment and diagnositc equipment, conduit, wound care and medical dressing, scar is cured, and delivery system.
Embodiment
Below in conjunction with embodiment and comparative example, the present invention will be further described.In the following Examples and Comparative Examples, represent anti-microbial property with reduction ratio, this numerical value is higher, illustrates that anti-microbial property is stronger.
In following examples and comparative example, germ resistance test adopts AATCC 100/ film contacts method, sample be containing the sulfuration of different concns antiseptic-germicide or carboxylic acid after silicon rubber, operation steps is as follows:
1. silicon rubber film and streptococcus aureus and intestinal bacteria are inoculated, cultivate 18-24 hour;
2. make it reach 10 by spectrophotometric standards test microbes 8group;
3. obtain about 1-5x10 with 0.2% nutrient broth and stroke-physiological saline solution dilution test microorganism 5group;
4. inoculation test sample: sample is cut into the fritter sample of 35 millimeters * 35 millimeters and the streptococcus aureus of 0.4 milliliter and intestinal bacteria and inoculates respectively;
5. at the temperature of 36-38 DEG C, every block sample is placed in the aseptic petri diss of 60 millimeters, swims in another 100 millimeters and takes advantage of in the culture dish filling sterilized water of 20 millimeters and cultivate 24 hours, record bacterial number at zero point;
After 6.24 hours, sample and meat soup neutralized and progressively dilutes, recording bacterial number after 24 hours.
Form 1 shows sample silicon rubber A only containing nano-silver water solution, does not add the result of carboxylic acid in germ resistance test, all without germ resistance.
Form 1
Form 2 shows sample silicon rubber B only containing silver zirconium phosphate RC2000 hydrogen sodium, does not add the result of carboxylic acid in germ resistance test, all without germ resistance.
Form 2
Form 3 shows sample silicon rubber A only containing silver-colored ceramic base, does not add the result of carboxylic acid in germ resistance test, all without germ resistance.
Form 3
Form 4 shows sample silicon rubber B only containing the silver ions additive doing carrier with ceramic particle, does not add the result of carboxylic acid in germ resistance test, all without germ resistance.
Form 4
Form 5 shows a kind of liquid silastic prepared by the formula of this invention, demonstrates efficient germ resistance and surperficial silver ions activity after test.
Form 5
Form 6 shows when carboxylic acid is used alone, and when namely not adding containing silver additive, does not also have germ resistance.See the contrast sample 13 in form 6, contrast sample 14.And when using together with RC2000 antiseptic-germicide, namely demonstrate the germ resistance of height, see the sample 2 in form and sample 3.
Form 6
Form 7 shows when carboxylic acid is used alone, and when namely not adding containing silver additive, does not also have germ resistance.See the contrast sample 15 in form 7, contrast sample 16.And when using together with RC2000 antiseptic-germicide, namely demonstrate the germ resistance of height, see the sample 4 in form and sample 5.
Form 7
Form 8 provides the result of another kind of high viscosity silicone rubber formulations test, all demonstrates the associating reinforced effects of same carboxylic acid and silver-containing antibacterial agent.
Form 8
The combination of above-mentioned data presentation silver-containing antibacterial agent and carboxylic acid can improve the antibacterial effect of common silver-containing antibacterial agent in silicon rubber, greatly sometimes from completely invalid to the sterilization effect of the high order of magnitude.Meanwhile, data also show, this be combined in liquid silastic and high viscosity formula in all applicable.

Claims (8)

1. an antimicrobial silicon rubber, comprises by weight percentage:
Silicon rubber 96.5-98%
The antimicrobial additive 0.1-10% of silver ion
Carboxylic acid 0.1-5%.
2. antimicrobial silicon rubber according to claim 1, is characterized in that: comprise by weight percentage:
Silicon rubber 96.5-98%
The antimicrobial additive 0.2-5% of silver ion
Carboxylic acid 0.2-3%.
3. antimicrobial silicon rubber according to claim 2, is characterized in that: comprise by weight percentage:
Silicon rubber 96.5-98%
The antimicrobial additive 0.5-2% of silver ion
Carboxylic acid 0.5-2%.
4. the antimicrobial silicon rubber according to claim 1-3, is characterized in that: described silicon rubber comprises high viscosity silicon rubber and liquid silastic.
5. antimicrobial silicon rubber according to claim 4, is characterized in that: the glass particle that the antimicrobial additive of described silver ion comprises silver-loaded zirconium phosphate, silver carboxylate, silver-impregnated zeolite, top coat carry silver, colloidal metal Argent grain or nano metal Argent grain one or more.
6. antimicrobial silicon rubber according to claim 5, is characterized in that: described carboxylic acid comprises one or more of acid anhydrides of single acid, bisgallic acid, triprotic acid, lipid acid, alicyclic acid, alicyclic acid aromatic carboxylic acid or above-mentioned carboxylic acid.
7. antimicrobial silicon rubber according to claim 6, is characterized in that: when described carboxylic acid is saturated fatty acid, the amount of carbon atom of described carboxylic acid is no more than 14; When described carboxylic acid has a unsaturated double-bond, the amount of carbon atom of described carboxylic acid is no more than 20.
8. prepare the method for antimicrobial silicon rubber described in claim 7, it is characterized in that the method comprises the following steps:
A) component A of liquid silastic, the antimicrobial additive of silver ion and carboxylic acid are mixed by corresponding weight percent;
B) add platinum catalyst, at room temperature stir 30-90min;
C) sulfidization molding is mixed with the B component of liquid silastic.
Or
A) antimicrobial additive of high viscosity silicon rubber, silver ion and carboxylic acid are mixed in mixing roll by corresponding weight percent;
B) platinum catalyst is added, at room temperature mixing 30-90min;
C) sulfidization molding.
CN201510165646.XA 2015-04-08 2015-04-08 Antibacterial silicone rubber and preparation method thereof Pending CN104725864A (en)

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Application Number Priority Date Filing Date Title
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105368055A (en) * 2015-12-03 2016-03-02 中南大学 Preparation method of modified antibacterial silicone rubber
CN105400200A (en) * 2015-12-03 2016-03-16 中南大学 Method for preparing antibacterial silicone rubber
CN105907099A (en) * 2016-06-27 2016-08-31 林春梅 Antibacterial catheter material and preparing method thereof
CN106178144A (en) * 2016-07-07 2016-12-07 腾科宝迪(厦门)生物科技有限公司 Single use incision protective sleeve and preparation method thereof
CN107412841A (en) * 2017-08-09 2017-12-01 江西高大生物医疗科技有限公司 A kind of production method of medical tea oil dressing
CN107501949A (en) * 2017-09-21 2017-12-22 河南驼人医疗器械集团有限公司 A kind of medical antibacterial silica gel material and preparation method thereof
CN109438994A (en) * 2018-11-09 2019-03-08 宁波隆盛硅业有限公司 A kind of antibacterial silicon rubber and its production technology and production system
CN110591362A (en) * 2019-09-04 2019-12-20 深圳市圆方科技新材料有限公司 Antibacterial handle sheath
CN112515242A (en) * 2020-10-22 2021-03-19 深圳雪雾科技有限公司 Cigarette cartridge shell, preparation method thereof, cigarette cartridge and electronic cigarette

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101627082A (en) * 2007-02-20 2010-01-13 道康宁公司 Filler treating agents based on hydrogen bonding polyorganosiloxanes
CN102014637A (en) * 2008-02-26 2011-04-13 莫门蒂夫性能材料股份有限公司 Silicone rubber exhibiting effective antimicrobial activity
CN104169335A (en) * 2012-01-04 2014-11-26 莫门蒂夫性能材料股份有限公司 Curable compositions of ionic silicones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101627082A (en) * 2007-02-20 2010-01-13 道康宁公司 Filler treating agents based on hydrogen bonding polyorganosiloxanes
CN102014637A (en) * 2008-02-26 2011-04-13 莫门蒂夫性能材料股份有限公司 Silicone rubber exhibiting effective antimicrobial activity
CN104169335A (en) * 2012-01-04 2014-11-26 莫门蒂夫性能材料股份有限公司 Curable compositions of ionic silicones

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105368055A (en) * 2015-12-03 2016-03-02 中南大学 Preparation method of modified antibacterial silicone rubber
CN105400200A (en) * 2015-12-03 2016-03-16 中南大学 Method for preparing antibacterial silicone rubber
CN105907099A (en) * 2016-06-27 2016-08-31 林春梅 Antibacterial catheter material and preparing method thereof
CN106178144A (en) * 2016-07-07 2016-12-07 腾科宝迪(厦门)生物科技有限公司 Single use incision protective sleeve and preparation method thereof
CN107412841A (en) * 2017-08-09 2017-12-01 江西高大生物医疗科技有限公司 A kind of production method of medical tea oil dressing
CN107501949A (en) * 2017-09-21 2017-12-22 河南驼人医疗器械集团有限公司 A kind of medical antibacterial silica gel material and preparation method thereof
CN109438994A (en) * 2018-11-09 2019-03-08 宁波隆盛硅业有限公司 A kind of antibacterial silicon rubber and its production technology and production system
CN110591362A (en) * 2019-09-04 2019-12-20 深圳市圆方科技新材料有限公司 Antibacterial handle sheath
CN112515242A (en) * 2020-10-22 2021-03-19 深圳雪雾科技有限公司 Cigarette cartridge shell, preparation method thereof, cigarette cartridge and electronic cigarette

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Application publication date: 20150624