CN1310588C - Composite antibacterial agent and its preparation method - Google Patents
Composite antibacterial agent and its preparation method Download PDFInfo
- Publication number
- CN1310588C CN1310588C CNB2005100129494A CN200510012949A CN1310588C CN 1310588 C CN1310588 C CN 1310588C CN B2005100129494 A CNB2005100129494 A CN B2005100129494A CN 200510012949 A CN200510012949 A CN 200510012949A CN 1310588 C CN1310588 C CN 1310588C
- Authority
- CN
- China
- Prior art keywords
- type zeolite
- vpi
- mcm
- antibacterial agent
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention provides a composite antibacterial agent and a preparation method thereof, particularly an organic-inorganic composite antibacterial agent and a preparation method, which belongs to the technical field of material science and engineering research. The present invention is characterized in that an organic-inorganic composite antibacterial agent combines an organic antibacterial agent with an inorganic antibacterial agent with a porous structure, namely that an 8-hydroxyquinoline organic antibacterial agent is combined with an X, Y, beta, VPI-5 or MCM-41 zeolite inorganic antibacterial agent which has a porous structure and contains one or several kinds of silver ion, zinc ion and copper ion. The present invention has the advantages of strong mildew and virus killing and inhibiting ability, high sterilization speed, high thermal stability, safety and long effective time.
Description
Technical field
A kind of complex antimicrobials of the present invention and preparation method thereof belongs to the Materials Science and Engineering research field, is specifically related to a kind of organic and inorganic complex antimicrobials and preparation method.
Background technology
The research of organic and inorganic complex antimicrobials is at the early-stage, and the research report of relevant its preparation method and application is less.At present, comparatively typical organic and inorganic complex antimicrobials, be to be parent with material with layer structure, utilize interlayer to insert reaction, make between complex compound implant layer, all adopt montmorillonite as carrier as A.Oya etc. and bridge Wen Yan etc., after argent ion and organic antibacterial agent 2-(4-thiazolyl) benzimidazole (TBZ) complexing organic antibacterial agent and argent ion, add in the montmorillonite layer, made bacterium and all effective organic and inorganic complex antimicrobials of mould.Though the antibacterial agent that this method makes has characteristics such as good stability, life-span length, antimicrobial efficiency height, complicated process of preparation, and range of application is narrower, only is applicable to that energy and silver ion form the organic antibacterial agent of complex compound and the inorganic antiseptic with layer structure.Konagaya, the patent of invention of Shigeji etc. (US6013275) adopts carries out composite method with organic antibacterial agent and inorganic antiseptic and hydroaropic substance and prepares the organic and inorganic complex antimicrobials, its preparation process is, make organic antibacterial agent and hydroaropic substance form copolymer earlier, and then with the inorganic antiseptic blend.Though preparation technology is simple for this method, be applicable to all organic and inorganic antiseptics, and can improve the anti-microbial property of complex antimicrobials in a short time, can not solve organic antibacterial agent poor heat resistance, short shortcoming of life-span effectively.
Summary of the invention:
A kind of complex antimicrobials of the present invention and preparation method thereof purpose is, overcome the problem and the defective that exist in above-mentioned existing antibacterial agent and preparation method thereof, provide a kind of and kill to press down mould, virus capable is strong, anti-sterilization speed is fast, heat endurance, safety and long-lasting good organic and inorganic complex antimicrobials and preparation method thereof.
A kind of complex antimicrobials of the present invention, it is characterized in that it being a kind of organic and inorganic complex antimicrobials that organic antibacterial agent is assembled in the inorganic antiseptic with meso-hole structure, promptly be that a kind of organic antibacterial agent oxine is assembled in has meso-hole structure, contain a kind of organic and inorganic complex antimicrobials in one or more X, Y, β, VPI-5 or the MCM-41 type zeolite inorganic antiseptic in silver, zinc, the copper ion, its structural formula can be represented by the formula:
M-(8-HQ)
n/Z
Wherein: M represents antibacterial metal ions, i.e. one or more in silver, zinc, the copper ion;
8-HQ represents the organic antibacterial agent oxine, and its chemical molecular formula is HOC
6H
3N:CHCH:CH;
N represents the molecule number of 8-HQ, and is relevant with kind and the ioni valence of M;
Z represents the carrier of inorganic antiseptic, i.e. a kind of in X, Y, β, VPI-5 or the MCM-41 type zeolite.
The preparation method of above-mentioned a kind of complex antimicrobials is characterized in that adopting the free ligand legal system to have machine-inorganic complex antimicrobials:
I. the preparation of inorganic antiseptic
(a) preparation of Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent
With each 40～60g of X, Y, β, VPI-5 or MCM-41 type zeolite powder, join respectively and have agitating device, filling 1L concentration is 0.03-0.10mol/L AgNO
3In the reactor of solution, in temperature is 50～70 ℃, the pH value is under 6～8 the lucifuge condition, stirring reaction 3～5h, make zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions, reaction is carried out centrifugation after finishing, with isolated solid sample distilled water wash, under 90～110 ℃ temperature condition, dry then, promptly make Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent.
(b) preparation of carrying silver-colored zinc or carrying silver-bearing copper X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent
Each 40～60g of Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent powder that will make by above-mentioned technology joins respectively and has agitating device, and filling 1L concentration is 0.10-0.40mol/LZn (NO
3)
2Or Cu (NO
3)
2In the reactor of solution, be 50 ℃～70 ℃ in temperature, the pH value is that stirring reaction 4～6h makes Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent and zinc nitrate or copper nitrate solution generation ion-exchange reactions under 6～8 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 90～110 ℃ temperature condition then, promptly makes to carry silver-colored zinc or carry silver-bearing copper X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent.
II. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 0.5-2.0mmol/L.
III. the preparation of organic and inorganic complex antimicrobials
(a) preparation of oxine silver/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials
With each 40～60g of Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent, join respectively and fill in the ethanolic solution of oxine that 1L concentration is 0.5-2.0mmol/L, in 0～70 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials (being designated as Ag-(8-HQ)/X, Y, β, VPI-5 or MCM-41 type zeolite);
(b) preparation of oxine silver zinc or silver-bearing copper/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials:
To carry silver-colored zinc or carry each 40～60g of silver-bearing copper X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent, join respectively and fill in the ethanolic solution of oxine that 1L concentration is 0.5-2.0mmol/L, in 0～70 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver zinc or silver-bearing copper/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials, be designated as AgZn-(8-HQ)
3/ X, Y, β, VPI-5 or MCM-41 type zeolite or AgCu-(8-HQ)
3/ X, Y, β, VPI-5 or MCM-41 type zeolite.
The invention has the advantages that by implementing technique scheme, organic antibacterial agent is assembled in the inorganic antiseptic with meso-hole structure, its heat endurance is improved a lot, improved 106 ℃ nearly; Because " shielding " of Zeolite support acts on, the resistance to light of organic antibacterial agent and long-lastingly also increase.Simultaneously, because the adding of organic antibacterial agent, the ability and the anti-sterilization speed that make inorganic antiseptic press down mould, virus have extremely obtained raising by a relatively large margin.To Escherichia coli, inorganic antiseptic is generally after the 6h action time under identical condition, excellent antibacterial effect can occur, and this organic and inorganic complex antimicrobials only needs 15min, but 100% kill effect just occurred.The present invention compares with the preparation method of existing organic and inorganic complex antimicrobials, realized the organic assembling on organic antibacterial agent and the inorganic antiseptic 26S Proteasome Structure and Function, made the heat resistance, resistance to light, safety, long-lasting and kill the ability that presses down mould, virus and anti-sterilization speed by a relatively large margin raising is all arranged of this complex antimicrobials.Technology of the present invention is simple, and is easy to operate, and can be applied to various organic antibacterial agents is that the inorganic antiseptic of carrier prepares in the middle of the process of organic and inorganic complex antimicrobials with having the meso-hole structure material, carries out large-scale industrial production.Product can be applicable to all conglomeraties and fields such as antibiotic plastic, anti-bacterial fibre, antibiotic paint.
Embodiment:
Below in conjunction with embodiment the present invention is made further instruction
Embodiment 1:
I. the preparation of Dan Zaiyin X type zeolite antibacterial agent
X type zeolite powder 40g joined have agitating device, filling 1L concentration is 0.03mol/LAgNO
3In the reactor of solution, be 50 ℃ in temperature, the pH value is that stirring reaction 4h makes zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions under 6 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 90 ℃ temperature condition then, promptly makes Dan Zaiyin X type zeolite antibacterial agent.
II. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 0.5mmol/L.
The preparation of III.8-oxyquinoline silver/X type Zeolite organic-inorganic complex antimicrobials
With each 40g of Dan Zaiyin X type zeolite antibacterial agent, join and fill in the ethanolic solution of oxine that 1L concentration is 0.5mmol/L, in 0 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver/X type Zeolite organic-inorganic complex antimicrobials (being designated as Ag-(8-HQ)/X type zeolite).
Embodiment 2:
I. the preparation of Dan Zaiyin y-type zeolite antibacterial agent
Y-type zeolite powder 50g joined have agitating device, filling 1L concentration is 0.05mol/LAgNO
3In the reactor of solution, be 60 ℃ in temperature, the pH value is that stirring reaction 5h makes zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions under 7 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 100 ℃ temperature condition then, promptly makes Dan Zaiyin y-type zeolite antibacterial agent.
II. carry the preparation of silver-colored zinc y-type zeolite antibacterial agent
The Dan Zaiyin y-type zeolite antibacterial agent powder 50g that will make by above-mentioned technology joins and has agitating device, and filling 1L concentration is 0.10mol/L Zn (NO
3)
2In the reactor of solution, be 60 ℃ in temperature, the pH value is that stirring reaction 5h makes Dan Zaiyin y-type zeolite antibacterial agent and zinc nitrate solution generation ion-exchange reactions under 7 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 100 ℃ temperature condition then, promptly makes to carry silver-colored zinc y-type zeolite antibacterial agent.
III. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 1.0mmol/L.
The preparation of IV.8-oxyquinoline silver zinc y-type zeolite organic and inorganic complex antimicrobials
Join and fill in the ethanolic solution of oxine that 1L concentration is 1.0mmol/L carrying silver-colored zinc y-type zeolite antibacterial agent 50g, in 20 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver zinc y-type zeolite organic and inorganic complex antimicrobials and (be designated as AgZn-(8-HQ)
3/ y-type zeolite).
Embodiment 3:
I. the preparation of Dan Zaiyin zeolite beta antibacterial agent
Zeolite beta powder 60g joined have agitating device, filling 1L concentration is 0.07mol/LAgNO
3In the reactor of solution, be 70 ℃ in temperature, the pH value is that stirring reaction 6h makes zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions under 8 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 110 ℃ temperature condition then, promptly makes Dan Zaiyin zeolite beta antibacterial agent.
II. carry the preparation of silver-bearing copper zeolite beta antibacterial agent
The Dan Zaiyin zeolite beta antibacterial agent powder 60g that will make by above-mentioned technology joins and has agitating device, and filling 1L concentration is 0.20mol/L Cu (NO
3)
2In the reactor of solution, be 70 ℃ in temperature, the pH value is that stirring reaction 6h makes Dan Zaiyin zeolite beta antibacterial agent and copper nitrate solution generation ion-exchange reactions under 8 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 110 ℃ temperature condition then, promptly makes to carry silver-bearing copper zeolite beta antibacterial agent.
III. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 1.5mmol/L.
The preparation of IV.8-oxyquinoline silver-bearing copper zeolite beta organic and inorganic complex antimicrobials
Join and fill in the ethanolic solution of oxine that 1L concentration is 1.5mmol/L carrying silver-bearing copper zeolite beta antibacterial agent 60g, in 35 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver-bearing copper zeolite beta organic and inorganic complex antimicrobials and (be designated as AgCu-(8-HQ)
3/ zeolite beta).
Embodiment 4:
I. the preparation of Dan Zaiyin VPI-5 type zeolite type zeolite antibacterial agent
VPI-5 type zeolite powder 50g joined have agitating device, filling 1L concentration is 1.0mol/LAgNO
3In the reactor of solution, be 60 ℃ in temperature, the pH value is that stirring reaction 4h makes zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions under 7 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 100 ℃ temperature condition then, promptly makes Dan Zaiyin VPI-5 type zeolite antibacterial agent.
II. carry the preparation of silver-colored zinc VPI-5 type zeolite antibacterial agent
The Dan Zaiyin VPI-5 type zeolite antibacterial agent powder 50g that will make by above-mentioned technology joins and has agitating device, and filling 1L concentration is 0.30mol/L Zn (NO
3)
2In the reactor of solution, be 60 ℃ in temperature, the pH value is that stirring reaction 4h makes Dan Zaiyin VPI-5 type zeolite antibacterial agent and zinc nitrate solution generation ion-exchange reactions under 7 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 100 ℃ temperature condition then, promptly makes to carry silver-colored zinc VPI-5 type zeolite antibacterial agent.
III. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 2.0mmol/L.
The preparation of IV.8-oxyquinoline silver zinc VPI-5 type Zeolite organic-inorganic complex antimicrobials
Join and fill in the ethanolic solution of oxine that 1L concentration is 2.0mmol/L carrying silver-colored zinc VPI-5 type zeolite antibacterial agent 50g, in 50 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver zinc VPI-5 type Zeolite organic-inorganic complex antimicrobials and (be designated as AgZn-(8-HQ)
3/ VPI-5 type zeolite).
Embodiment 5:
I. the preparation of Dan Zaiyin MCM-41 type zeolite type zeolite antibacterial agent
MCM-41 type zeolite powder 50g joined have agitating device, filling 1L concentration is 0.05mol/LAgNO
3In the reactor of solution, be 50 ℃ in temperature, the pH value is that stirring reaction 4h makes zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions under 7 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 100 ℃ temperature condition then, promptly makes Dan Zaiyin MCM-41 type zeolite antibacterial agent.
II. carry the preparation of silver-bearing copper MCM-41 type zeolite antibacterial agent
The Dan Zaiyin MCM-41 type zeolite antibacterial agent powder 50g that will make by above-mentioned technology joins and has agitating device, and filling 1L concentration is 0.40mol/L Cu (NO
3)
2In the reactor of solution, be 60 ℃ in temperature, the pH value is that stirring reaction 4h makes Dan Zaiyin MCM-41 type zeolite antibacterial agent and copper nitrate solution generation ion-exchange reactions under 7 the lucifuge condition.Reaction is carried out centrifugation after finishing, and with isolated solid sample distilled water wash, dries under 100 ℃ temperature condition then, promptly makes to carry silver-bearing copper MCM-41 type zeolite antibacterial agent.
III. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 1.5mmol/L.
The preparation of IV.8-oxyquinoline silver-bearing copper MCM-41 type Zeolite organic-inorganic complex antimicrobials
Join and fill in the ethanolic solution of oxine that 1L concentration is 1.5mmol/L carrying silver-bearing copper MCM-41 type zeolite antibacterial agent 50g, in 50 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till.Promptly make oxine silver-bearing copper MCM-41 type Zeolite organic-inorganic complex antimicrobials and (be designated as AgCu-(8-HQ)
3/ MCM-41 type zeolite).
Claims (2)
1. complex antimicrobials, it is characterized in that it being a kind of organic and inorganic complex antimicrobials that organic antibacterial agent is assembled in the inorganic antiseptic with meso-hole structure, promptly be that a kind of organic antibacterial agent oxine is assembled in has meso-hole structure, contain a kind of organic and inorganic complex antimicrobials in one or more X, Y, β, VPI-5 or the MCM-41 type zeolite inorganic antiseptic in silver, zinc, the copper ion, its structural formula can be represented by the formula:
M-(8-HQ)
n/Z
Wherein: M represents antibacterial metal ions, i.e. one or more in silver, zinc, the copper ion;
8-HQ represents the organic antibacterial agent oxine, and its chemical molecular formula is HOC
6H
3N:CHCH:CH;
N represents the molecule number of 8-HQ, and is relevant with kind and the ioni valence of M;
Z represents the carrier of inorganic antiseptic, i.e. a kind of in X, Y, β, VPI-5 or the MCM-41 type zeolite.
2. the preparation method of the described a kind of complex antimicrobials of claim 1 is characterized in that adopting the free ligand legal system to have machine-inorganic complex antimicrobials:
I. the preparation of inorganic antiseptic
(a) preparation of Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent
With each 40～60g of X, Y, β, VPI-5 or MCM-41 type zeolite powder, join respectively and have agitating device, filling 1L concentration is 0.03-0.10mol/L AgNO
3In the reactor of solution, in temperature is 50～70 ℃, the pH value is under 6～8 the lucifuge condition, stirring reaction 3～5h, make zeolite and liquor argenti nitratis ophthalmicus generation ion-exchange reactions, reaction is carried out centrifugation after finishing, with isolated solid sample distilled water wash, under 90～110 ℃ temperature condition, dry then, promptly make Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent;
(b) preparation of carrying silver-colored zinc or carrying silver-bearing copper X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent
Each 40～60g of Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent powder that will make by above-mentioned technology joins respectively and has agitating device, and filling 1L concentration is 0.10-0.40mol/L Zn (NO
3)
2Or Cu (NO
3)
2In the reactor of solution, in temperature is 50 ℃～70 ℃, the pH value is under 6～8 the lucifuge condition, stirring reaction 4～6h, make Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent and zinc nitrate or copper nitrate solution generation ion-exchange reactions, reaction is carried out centrifugation after finishing, with isolated solid sample distilled water wash, under 90～110 ℃ temperature condition, dry then, promptly make and carry silver-colored zinc or carry silver-bearing copper X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent;
II. the preparation of organic anti-bacterial agent solution
Press the ethanolic solution of the concentration preparation oxine of 0.5-2.0mmol/L;
III. the preparation of organic and inorganic complex antimicrobials
(a) preparation of oxine silver/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials
With each 40～60g of Dan Zaiyin X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent, join respectively and fill in the ethanolic solution of oxine that 1L concentration is 0.5-2.0mmol/L, in 0～70 ℃ temperature condition stir down be evaporated to dried, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till; Promptly make oxine silver/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials (being designated as Ag-(8-HQ)/X, Y, β, VPI-5 or MCM-41 type zeolite);
(b) preparation of oxine silver zinc or silver-bearing copper/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials:
To carry silver-colored zinc or carry each 40～60g of silver-bearing copper X, Y, β, VPI-5 or MCM-41 type zeolite antibacterial agent, join respectively and fill in the ethanolic solution of oxine that 1L concentration is 0.5-2.0mmol/L, stirring is evaporated to dried under 0～70 ℃ temperature condition, product through apparatus,Soxhlet's with the ethanol extracting to extract colourless till, promptly make oxine silver zinc or silver-bearing copper/X, Y, β, VPI-5 or MCM-41 type Zeolite organic-inorganic complex antimicrobials, be designated as AgZn-(8-HQ)
3/ X, Y, β, VPI-5 or MCM-41 type zeolite or AgCu-(8-HQ)
3/ X, Y, β, VPI-5 or MCM-41 type zeolite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100129494A CN1310588C (en) | 2005-10-28 | 2005-10-28 | Composite antibacterial agent and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100129494A CN1310588C (en) | 2005-10-28 | 2005-10-28 | Composite antibacterial agent and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1762219A CN1762219A (en) | 2006-04-26 |
| CN1310588C true CN1310588C (en) | 2007-04-18 |
Family
ID=36746699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100129494A Expired - Fee Related CN1310588C (en) | 2005-10-28 | 2005-10-28 | Composite antibacterial agent and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1310588C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5027452B2 (en) * | 2006-06-22 | 2012-09-19 | 株式会社シナネンゼオミック | Antibacterial zeolite particles and antibacterial resin composition |
| CN104312276A (en) * | 2014-11-10 | 2015-01-28 | 合肥宏图彩印有限公司 | Antibacterial heat-resistant special ink and preparation method thereof |
| CN107771855A (en) * | 2016-08-31 | 2018-03-09 | 天津天女化工集团股份有限公司 | A kind of antibacterial agent and the application in antibacterial UV ink |
| CN106633382A (en) * | 2016-10-19 | 2017-05-10 | 惠州市道科包装材料有限公司 | Compound anti-microbial master batch and preparation method thereof, anti-microbial plastic packaging product and preparation method thereof |
| CN108118558B (en) * | 2017-12-15 | 2020-07-28 | 浙江工业大学 | Plant essential oil loaded silver-zinc zeolite antibacterial paper pad and preparation method thereof |
| CN109169670A (en) * | 2018-11-22 | 2019-01-11 | 青岛中达农业科技有限公司 | 8-hydroxyquinoline zinc is preparing the purposes in disinfectant use in agriculture |
| CN110982450B (en) * | 2019-12-30 | 2021-07-13 | 肖可牧 | Waterproof antibacterial adhesive special for wooden products and preparation method thereof |
| CN112354067B (en) * | 2020-10-27 | 2022-08-26 | 医小邦(宁波)医疗科技有限公司 | Composite antibacterial catheter |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08119809A (en) * | 1994-10-27 | 1996-05-14 | Nippon Steel Chem Co Ltd | Carried 8-hydroxyquinolinecopper and its production |
| US6013275A (en) * | 1996-05-10 | 2000-01-11 | Toyo Boseki Kabushiki Kaisha | Antibacterial composition and antibacterial laminate |
-
2005
- 2005-10-28 CN CNB2005100129494A patent/CN1310588C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08119809A (en) * | 1994-10-27 | 1996-05-14 | Nippon Steel Chem Co Ltd | Carried 8-hydroxyquinolinecopper and its production |
| US6013275A (en) * | 1996-05-10 | 2000-01-11 | Toyo Boseki Kabushiki Kaisha | Antibacterial composition and antibacterial laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1762219A (en) | 2006-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1310588C (en) | Composite antibacterial agent and its preparation method | |
| CN1261268C (en) | Nanometer silver sol and preparing method thereof | |
| Gao et al. | A robust superhydrophobic antibacterial Ag–TiO2 composite film immobilized on wood substrate for photodegradation of phenol under visible-light illumination | |
| CN100451060C (en) | Chitosan/rectorite nano composite materials and method for preparing the same | |
| CN100336951C (en) | Antibacterial hollow activated carbon fiber of negative ion, and preparation method | |
| CN1752112A (en) | Montmorillonoid in-situ organises and prepares the method for nano composite polymer-montmorillonoid material | |
| CN101811664A (en) | Cellulose/silver nano composite material and preparation method thereof | |
| CN101041134A (en) | Modification bamboo charcoal having Ag and multihole TiO2 and the preparing method | |
| CN103891775B (en) | Zinc-carrying nano organic montmorillonite antimicrobial agent and preparation method thereof | |
| CN1749249A (en) | Chiral ionic liquid and its preparing method | |
| Sun et al. | Preparation of hemicellulose‐g‐poly (methacrylic acid)/carbon nanotube composite hydrogel and adsorption properties | |
| CN110075923A (en) | A kind of g-C3N4The bionical construction method and application thereof of/BiOI-pDA@PVDF photocatalysis membrana | |
| CN113292688B (en) | Preparation method of composite antibacterial agent and antibacterial plastic | |
| Emmanuel et al. | A pragmatic review on bio-polymerized metallic nano-architecture for photocatalytic degradation of recalcitrant dye pollutants | |
| CN1800260A (en) | Plymer base montmorillonite agglomerate and its preparation method | |
| CN101293980B (en) | Thermoplastic polyalcohol/clay soil nano-composite material, preparation method and application thereof | |
| CN1803898A (en) | Nanometer antibacterial plastic | |
| CN1310589C (en) | Method for preparing superfine composite inorganic antimicrobial agent | |
| CN111066784A (en) | Ag/AgCl/cellulose composite antibacterial material and preparation method and application thereof | |
| CN1287967A (en) | Surface preparation of layered dihydroxy composite metal oxide powder | |
| Zhang et al. | Construction of UiO-NH2@ TiC Schottky junction and their effectively photocatalytic and antibacterial performance | |
| CN1398520A (en) | Composite clay antiseptic and its prepn | |
| CN1262043A (en) | Bimetal Cu-Ag colloid as antibacterial agent and its preparing process | |
| CN1065880C (en) | Radiation graft process for preparing antiseptic material of pyridine salt type polymer | |
| Dai et al. | Layered double hydroxides for efficient treatment of heavy metals and organic pollutants: Recent progress and future perspectives |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |