CN101595880A - Complex antimicrobials and antimicrobial coating composition and antimicrobial coating material - Google Patents
Complex antimicrobials and antimicrobial coating composition and antimicrobial coating material Download PDFInfo
- Publication number
- CN101595880A CN101595880A CNA2008101106173A CN200810110617A CN101595880A CN 101595880 A CN101595880 A CN 101595880A CN A2008101106173 A CNA2008101106173 A CN A2008101106173A CN 200810110617 A CN200810110617 A CN 200810110617A CN 101595880 A CN101595880 A CN 101595880A
- Authority
- CN
- China
- Prior art keywords
- antimicrobial coating
- complex antimicrobials
- organic
- acid
- weight
- 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.)
- Granted
Links
Abstract
The invention provides a kind of complex antimicrobials, this complex antimicrobials contains inorganic antiseptic and organic antibacterial agent, wherein, described inorganic antiseptic is slaine and/or the metal oxide with antibacterial activity, described organic antibacterial agent is for having shown in following formula (I) and/or the formula (II) compound formed and in the pyridine one or more, in formula (I) and the formula (II), R
1And R
2Respectively do for oneself hydrogen or carbon number is the alkyl of 1-8.The antimicrobial coating material that the present invention also provides the antimicrobial coating composition that contains this complex antimicrobials and used this antimicrobial coating composition.Complex antimicrobials provided by the invention, the preparation method is very simple, only needs simply to mix and can reach extraordinary antibacterial effect forming the inorganic antiseptic of this complex antimicrobials and organic antibacterial agent.
Description
Technical field
The invention relates to a kind of complex antimicrobials and antimicrobial coating composition and antimicrobial coating material, in particular, be about a kind of complex antimicrobials and the antimicrobial coating material that contains the antimicrobial coating composition of this complex antimicrobials and used this antimicrobial coating composition.
Background technology
Along with the development of society and improving constantly of living standards of the people, people have higher requirement to the environmental quality and the health level of depending on for existence.Meanwhile, various pathogenic microorganismss are extensive in distributed in nature, and grow under certain condition, breed even make a variation, and can cause that not only the burn into of material decomposes, and also threatening human beings'health.Thereby, can more and more be subjected to people's favor to the antimicrobial product that health ensures to some extent.
And the core of antimicrobial product is the development of antibacterial agent, and common antibacterial agent has inorganic antiseptic, organic antibacterial agent.Advantage such as that inorganic antiseptic has is safe, good heat resistance, persistence are good, but have the shortcoming of antibiotic late effect property; Organic antibacterial agent general short-term antibiotic property height but poor durability.This shows that above-mentioned single type antibacterial agent is difficult to satisfy the existing market demand, thereby realize that spectrum truly is antibiotic.Therefore, the novel complex antimicrobials of development just more and more is subjected to people's attention.
At present, people have recognized the compound tense that carries out between the different antibacterial agents, need make complex antimicrobials produce synergy, synergy between the antibacterial agent is mainly reflected in when the overall low content of antibacterial agent can produce anti-microbial property, for example, disclosed a kind of nanometer inorganic-organic composite antibiotic material of CN 101120681A and its production and application, the chemical formula of described nanometer inorganic-organic composite antibiotic material are RE (A)
c(B)
dNH
2O; Wherein, RE represents rare earth ion, is La
3+, Ce
3+, Pr
3+, Nd
3 +, Sm
3+, Er
3+, Er
3+, Eu
3+, Y
3+, Dy
3+, Gd
3+In one or more, A is that amino acid, B are the azole heterocyclic compound, described azole heterocyclic compound is imidazoles or benzimidazole, c=1,2,3 or 4, d=1 or 2, n=1,2 or 3.The preparation method of this nanometer inorganic-organic composite antibiotic material may further comprise the steps:
1) in the nonaqueous solvents under 40-80 ℃ of temperature, according to rare earth ion: amino acid molar ratio is that 1: 2 to 1: 4 ratio feeds intake and the two backflow is stirred to sufficient reacting;
2) continue adding and be equivalent to the doubly alcoholic solution of the azole heterocyclic compound of mole of rare earth ion 2-4, stir, transfer pH to 5-8, continuation is stirred;
3) with the solution decompression distillation, the bottoms that obtain are fully washed with absolute ether and acetone,, obtain powdered product at 40-80 ℃ of following vacuum drying 4-10 hour.
Though disclosed complex antimicrobials can reach better anti-bacterial effect in the above-mentioned patent documentation when lower content, its preparation technology is complicated.
Summary of the invention
The objective of the invention is to overcome the defective of existing complex antimicrobials complicated process of preparation, a kind of antimicrobial coating material that can simply make and can produce synergistic complex antimicrobials and contain the antimicrobial coating composition of this complex antimicrobials and used this antimicrobial coating composition is provided.
The invention provides a kind of by simple just mixing of different antibacterial agents can be produced synergistic complex antimicrobials, promptly, the invention provides a kind of complex antimicrobials, this complex antimicrobials contains inorganic antiseptic and organic antibacterial agent, wherein, described inorganic antiseptic is slaine and/or the metal oxide with antibacterial activity, and described organic antibacterial agent is for having the compound of the composition shown in following formula (I) and/or the formula (II) and in the pyridine one or more:
R
1And R
2Respectively do for oneself hydrogen or carbon number is the alkyl of 1-8.
The present invention also provides a kind of antimicrobial coating composition, said composition contains organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid, antibacterial agent, curing agent and thinner, and curing agent does not coexist with other component, described organic complexing agent is the compound that contains two or more carbonyls, described polar organic solvent is that carbon number is the alcohol of 2-4, wherein, described antibacterial agent is a complex antimicrobials provided by the invention.
The present invention also provides a kind of antimicrobial coating material, this material comprises base material and is positioned at the antibiotic finishing coat of substrate surface, this antibiotic finishing coat obtains after being solidified by a kind of antimicrobial coating composition, and wherein, described antimicrobial coating composition is an antimicrobial coating composition provided by the invention.
Complex antimicrobials provided by the invention, the preparation method is very simple, only needs simply to mix and can reach extraordinary antibacterial effect forming the inorganic antiseptic of this complex antimicrobials and organic antibacterial agent.
Embodiment
The invention provides a kind of complex antimicrobials, this complex antimicrobials contains inorganic antiseptic and organic antibacterial agent, wherein, described inorganic antiseptic is slaine and/or the metal oxide with antibacterial activity, and described organic antibacterial agent is for having shown in following formula (I) and/or the formula (II) compound formed and in the pyridine one or more:
R
1And R
2Respectively do for oneself hydrogen or carbon number is the alkyl of 1-8.
Described carbon number is that the example of the alkyl of 1-8 comprises methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, as long as can make the compound of formula (I) or formula (II) have antibacterial activity.
Take all factors into consideration the being easy to get property and the antibacterial activity of raw material, described organic antibacterial agent is preferably one or more in isothiazolinone, benzisothiazole ketone and the pyridine, more preferably the mixture of isothiazolinone and benzisothiazole ketone.The present inventor finds, when described organic antibacterial agent is the mixture of isothiazolinone and benzisothiazole ketone, and the weight ratio of the mixture of isothiazolinone and benzisothiazole ketone is 1-5: 1,2-4 particularly: 1 o'clock, the particular significant effect of complex antimicrobials, the amount that reaches the required antibacterial agent of identical antibacterial effect can be low to moderate 0.03%.Therefore the more preferably described organic antibacterial agent of the present invention composition that is isothiazolinone and benzisothiazole ketone, the weight ratio of isothiazolinone and benzisothiazole ketone can be 1-5: 1, be preferably 2-4: 1.
According to the present invention, described inorganic antiseptic can be slaine and/or the metal oxide with antibacterial activity, for example can be one or more slaine and/or the metal oxide in silver, zinc, copper, lanthanum, cerium, praseodymium, neodymium, erbium, europium, yttrium, dysprosium and the gadolinium, preferred described inorganic antiseptic is one or more in silver salt, silver oxide, zinc salt, zinc oxide, mantoquita and the copper oxide, described silver salt, zinc salt and mantoquita respectively do for oneself citrate and/or nitrate.More preferably described inorganic antiseptic contains silver salt and/or silver oxide.According to this preferred implementation, can further improve the Synergistic antimicrobial effect of complex antimicrobials.
The weight ratio of described inorganic antiseptic and organic antibacterial agent can be 0.5-5: 1, be preferably 1-3: 1.
The present invention has no particular limits the preparation method of described complex antimicrobials, as long as inorganic antiseptic and organic antibacterial agent are mixed.
The present invention also provides a kind of antimicrobial coating composition, said composition contains organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid, antibacterial agent, curing agent and thinner, and curing agent does not coexist with other component, described organic complexing agent is the compound that contains two or more carbonyls, described polar organic solvent is that carbon number is the alcohol of 2-4, wherein, described antibacterial agent is a complex antimicrobials provided by the invention.
The present invention has no particular limits the content of complex antimicrobials in the described composition, is benchmark with the gross weight of composition, and the content of complex antimicrobials can be 0.03-10 weight %.Experiment showed, under the certain condition of the content of the complex antimicrobials in antibiotic finishing coat that when the thickness of antibiotic finishing coat was the 15-25 micron, the antibiotic rate of antimicrobial coating material did not change with the variation of the thickness of antibiotic finishing coat.Therefore when the thickness of the antibiotic finishing coat after described composition coating and the curing was the 15-25 micron, the content of complex antimicrobials can be 0.03-10 weight % in the described composition, is preferably 0.03-0.2 weight %; When the content of complex antimicrobials in the described composition was 0.03-0.2 weight %, the antibiotic rate that has applied the base material of this composite antibiosis colloidal sol can reach more than 95%; When the content of complex antimicrobials is higher than 0.2 weight %, raising along with the content of complex antimicrobials, antibiotic rate can increase, but effect and not obvious, simultaneously, along with the raising of the content of complex antimicrobials, its cost also correspondingly improves, therefore, consider that from the economy aspect content of complex antimicrobials is preferably 0.03-0.2 weight % in the described composition.In addition, gross weight with composition is a benchmark, the content of organosilicon described in the composition and organic titanium is 8-9 weight %, the content of described organic complexing agent is 2.5-3 weight %, the content of described polar organic solvent is 52.8-70 weight %, described inorganic acid and organic acid content are 2-3 weight %, and the content of described curing agent is 0.3-2 weight %, and the content of described thinner is 10-30 weight %.
Preferred organosilicon in organosilicon and the organic titanium, described organosilicon can be various esters of silicon acis, as long as have silicon-alkoxyl (Si-OR ', R ' is an alkyl) structure gets final product, be specifically as follows in ethyl orthosilicate, positive isopropyl silicate, vinyl silane triisopropoxide and the vinyltrimethoxy silane one or more, preferred vinyl three isopropoxy silane; Described organic titanium can be various titanate esters, gets final product as long as have titanium-alkoxyl (Ti-OR ', R ' is an alkyl) structure, is specifically as follows in tetraethyl titanate, isopropyl titanate and the tetrabutyl titanate one or more, preferred tetrabutyl titanate;
The preferred carbon number of described polar organic solvent is the alcohol of 2-4, and described carbon number is that the alcohol of 2-4 can be in methyl alcohol, ethanol, isopropyl alcohol and the n-butanol one or more, preferred alcohol; Described organic complexing agent can be 2 for containing two or more active carbonyl compounds, and one or more in 4-pentanedione, hydroresorcinol and the ethyl acetoacetate are preferred 2, the 4-pentanedione;
Preferred organic acid in organic acid and the inorganic acid, described inorganic acid can be in hydrochloric acid, sulfuric acid and the nitric acid one or more, preferred nitric acid; Described organic acid can be in acetate, citric acid and the tartaric acid one or more, optimization citric acid;
Described curing agent can be the curing agent that is used to make colloidal sol curing of routine, for example can be dibutyl tin laurate, ammonium acetate, 2, in the 4-diamino benzene sulfonic acid sodium one or more and 2, the mixture of 4-toluene di-isocyanate(TDI), wherein, in this mixture 2, the content of 4-toluene di-isocyanate(TDI) is 90-95 weight %, described thinner can be the viscosity that is used to regulate composition of routine, the solvent of control wet film rate of drying for example can be 1-Methoxy-2-propyl acetate and/or butyl acetate.
As those skilled in the known, when the outward appearance to antibiotic coating material has requirement, can also contain flatting silica in the described composition, flatting silica generally has delustring, transparent, thickening, anti-scratch flower and the effect that easily disperses, described flatting silica can be the flatting silica of routine, for example equally distributed micron that can make for the precipitation method or vapor phase method or in the nanometer grade silica one or more, for example can be for purchasing in sea, the Shanghai ease ACEMATT of the scientific ﹠ trading Co., Ltd. trade mark, the silica of the TS100 trade mark or the OK500 trade mark, gross weight with composition is a benchmark, and the consumption of described flatting silica is 0.2-5 weight %.
According to the present invention, in the described composition, curing agent can not with the coexistence of other composition because curing agent is during with the coexistence of other composition, can the generation curing reaction between the composition.Therefore, under non-working condition, curing agent independently exists.Generally, described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid and complex antimicrobials can be present in first component, thinner is present in second component, and curing agent is present in the 3rd component; Wherein, described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid and complex antimicrobials mix and are the stable sols shape, before the use, in colloidal sol, add the viscosity that thinner is regulated colloidal sol earlier, add curing agent again and mix, can apply.
Perhaps described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid, complex antimicrobials and thinner are present in the same component, curing agent is present in another component; Wherein, described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid, complex antimicrobials and mixing diluents evenly are the stable sols shape, add curing agent before using and mix, and can apply.
Perhaps also can directly each component in the composition be mixed the back coating before use.
Dual mode before preferred, promptly described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid and complex antimicrobials are present in first component, and thinner is present in second component, and curing agent is present in the 3rd component; Perhaps described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid, complex antimicrobials and thinner are present in the same component, and curing agent is present in another component.The antibacterial effect of the antimicrobial coating composition of this preferred dual mode is better.
The present invention also provides a kind of antimicrobial coating material, this material comprises base material and is positioned at the antibiotic finishing coat of substrate surface, this antibiotic finishing coat obtains after being solidified by a kind of antimicrobial coating composition, and wherein, described antimicrobial coating composition is an antimicrobial coating composition provided by the invention.
Be coated on the base material after during use described composition and water being mixed and get final product, described on base material the method for coating composition can be the coating method of routine, for example can directly apply or spray, consider from the adhesive force aspect between composition and the base material, the method of preferred spraying, for example can spray with spray gun, in addition, as those skilled in the known, particle in the composition is more little, and the adhesive force between composition and the base material is good more, therefore, preferably before spraying, earlier composition is crossed 500-600 purpose filter cloth.
The method that the described composition that will be coated on the base material solidifies can for example can be that heat cure or UV solidify for well known to a person skilled in the art method, and heat cure can be 70-90 ℃ of baking 15-45 minute down; UV solidifies can be for shining 30-120 second with ultraviolet light from antibiotic finishing coat surface, and the UV condition of cure comprises that the ultraviolet light intensity is a 1000-1300 milli Jiao/square centimeter, wave-length coverage 360-370 nanometer, and sample and light source distance are 25-100 centimetre.
The present invention has no particular limits the thickness of described antibiotic finishing coat, in general, have certain resistance to marring in order to make substrate surface, the thickness that requires the overlay of substrate surface is the 15-25 micron, therefore, the thickness of described antibiotic finishing coat can be the 15-25 micron.
Under the preferable case, described antimicrobial coating material can also comprise between base material and antibiotic finishing coat, be used to improve the overlay of substrate surface and the adhesive force between the base material priming coat, the thickness of described priming coat can be the 8-12 micron.Described priming coat can be the overlay that can improve substrate surface of routine and the coating of the adhesive force between the base material, be conventionally known to one of skill in the art, generally can be for containing the priming paint of polyurethanes compound, for example can coat with lacquer, or purchase in the thermosetting of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark and coat with lacquer for purchasing in the thermosetting of Akzo Nobel's coating SC-J-B14121 of Co., Ltd trade mark.
The present invention has no particular limits the method that forms priming coat on base material, can be the method for routine, and is concrete identical with the method for coating composition on base material, do not repeat them here, different is preferably before spraying, earlier composition to be crossed 300-400 purpose filter cloth.
As those skilled in the known, behind coating priming coat on the base material, priming coat is solidified, described curing can be heat cure, and the method for described heat cure is conventional method, for example can toast 5-15 minute down at 70-90 ℃.
When the color to base material had requirement, described antimicrobial coating material can also comprise between priming coat and antibiotic finishing coat, be used to regulate the floating coat of the color of antimicrobial coating material, and the thickness of described floating coat can be the 10-15 micron.Described floating coat can for the color that can regulate substrate surface of routine and improve priming coat and antibiotic finishing coat between the coating of adhesive force, be conventionally known to one of skill in the art, generally can be for containing the colored paint of polyurethanes compound, for example can coat with lacquer, or purchase in the thermosetting of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark and coat with lacquer for purchasing in the thermosetting of Akzo Nobel's coating SC-D-Z24072 of Co., Ltd trade mark.Wherein, purchase in the thermosetting lacquer and the adhesive force between base material and the antibiotic finishing coat of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark all better, therefore purchase when the thermosetting of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark is coated with lacquer when priming coat and floating coat are, priming coat and floating coat are one deck.
The present invention has no particular limits the method that forms floating coat on priming coat, can be the method for routine, and is concrete identical with the method for coating composition on base material, do not repeat them here, different is preferably before spraying, earlier composition to be crossed 400-500 purpose filter cloth.
As those skilled in the known, behind coating floating coat on the priming coat, floating coat is solidified, described curing can be heat cure, and the method for described heat cure is conventional method, for example can toast 5-15 minute down at 70-90 ℃.
Described base material can be acrylonitrile/butadiene/styrene copolymer (ABS), polypropylene (PP), Merlon (PC) and their complex, or stainless steel, titanium, magnesium, aluminium, zinc and their alloy.
Adopt specific embodiment that the present invention is further elaborated below.
Embodiment 1
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
(1) preparation complex antimicrobials
10 gram inorganic antiseptics (5 gram silver citrates and 5 gram zinc citrates) and 10 gram organic antibacterial agents (7 gram isothiazolinone and 3 gram benzisothiazole ketone) are mixed, be complex antimicrobials A1 of the present invention.
(2) preparation antimicrobial coating composition
With complex antimicrobials, 8 gram vinyl silane triisopropoxides, 2.5 grams 2 of the above-mentioned preparation of 10 grams, 4-pentanedione, 67 gram ethanol, 2 gram citric acids and 0.2 gram flatting silica (sea, the Shanghai ease TS100 of scientific ﹠ trading Co., Ltd.) mix, and are the colloidal sol shape.
Add 10 gram 1-Methoxy-2-propyl acetates and mix in the colloidal sol of above-mentioned preparation, add 0.27 gram 2 again, 4-toluene di-isocyanate(TDI), 0.03 gram dibutyl tin laurate mix and promptly obtain composition.
(3) preparation antimicrobial coating material
20 grams are purchased after 300 order filter clothes were coated with lacquer in the thermosetting of Akzo Nobel's coating SC-J-B14121 of Co., Ltd trade mark, be sprayed onto on stainless steel substrate (the sharp emerging stainless steel BS/SUS304-O of the Co., Ltd trade mark in the Ningbo) surface with spray gun, 70 ℃ of bakings 15 minutes, formation thickness was 10 microns priming coat on base material then.
25 grams are purchased after 400 order filter clothes were coated with lacquer in the thermosetting of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat with spray gun, 70 ℃ of bakings 15 minutes, formation thickness was 12 microns floating coat on base material then.
With 50 the gram above-mentioned preparation compositions cross 500 order filter clothes after, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat and floating coat successively with spray gun, 70 ℃ of bakings 45 minutes, formation thickness was 25 microns antibiotic finishing coat on base material, promptly obtains antimicrobial coating material S1 then.
Embodiment 2
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
(1) preparation complex antimicrobials
30 gram inorganic antiseptics (30 gram silver citrate) and 10 gram organic antibacterial agents (8 gram isothiazolinone and 2 gram benzisothiazole ketone) are mixed, be complex antimicrobials A2 of the present invention.
(2) preparation antimicrobial coating composition
Complex antimicrobials, 9 gram ethyl orthosilicates, 3 gram hydroresorcinols, 52.8 gram isopropyl alcohols, 3 gram tartaric acid and the 30 gram butyl acetates of the above-mentioned preparation of 0.2 gram are mixed, be the colloidal sol shape.
Add 1.9 grams 2 in the colloidal sol of above-mentioned preparation, 4-toluene di-isocyanate(TDI), 0.1 gram ammonium acetate mix and promptly obtain composition.
(3) preparation antimicrobial coating material
15 grams are purchased after 400 order filter clothes were coated with lacquer in the thermosetting of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark, be sprayed onto on polycarbonate substrate (U.S. EXL1414 of the GE company trade mark) surface with spray gun, 80 ℃ of bakings 10 minutes, formation thickness was 8 microns priming coat on base material then.
20 grams are purchased after 500 order filter clothes were coated with lacquer in the thermosetting of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark, be sprayed onto on the above-mentioned polypropylene base surface that is formed with priming coat with spray gun, 80 ℃ of bakings 10 minutes, formation thickness was 10 microns floating coat on base material then.
With 30 the gram above-mentioned preparation compositions cross 600 order filter clothes after, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat and floating coat successively with spray gun, 90 ℃ of bakings 15 minutes, formation thickness was 15 microns antibiotic finishing coat on base material, promptly obtains antimicrobial coating material S2 then.
Embodiment 3
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
(1) preparation complex antimicrobials
20 gram inorganic antiseptics (10 gram silver citrates, 5 gram zinc oxide and 5 gram copper nitrates) and 10 gram organic antibacterial agents (7.5 gram isothiazolinone and 2.5 gram benzisothiazole ketone) are mixed, be complex antimicrobials A3 of the present invention.
(2) preparation antimicrobial coating composition
Complex antimicrobials, the positive isopropyl silicate of 8.5 grams, 2.8 gram ethyl acetoacetates, 60.17 gram n-butanols, 2.5 gram nitric acid, 5 gram flatting silicas (sea, the Shanghai ease OK500 of scientific ﹠ trading Co., Ltd.), 0.92 gram 2 with the above-mentioned preparation of 0.03 gram, 4-toluene di-isocyanate(TDI), 0.08 gram 2,4-diamino benzene sulfonic acid sodium and 20 gram butyl acetates mix, and promptly obtain composition.
(3) preparation antimicrobial coating material
25 grams are purchased after 300 order filter clothes were coated with lacquer in the thermosetting of Akzo Nobel's coating SC-J-B14121 of Co., Ltd trade mark, be sprayed onto on the magnesium substrates surface with spray gun, then 90 ℃ of bakings 15 minutes, formation thickness is 12 microns priming coat on base material.
30 grams are purchased after 400 order filter clothes were coated with lacquer in the thermosetting of Akzo Nobel's coating SC-D-Z24072 of Co., Ltd trade mark, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat with spray gun, 90 ℃ of bakings 15 minutes, formation thickness was 15 microns floating coat on base material then.
With 40 the gram above-mentioned preparation compositions cross 500 order filter clothes after, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat and floating coat successively with spray gun, then with 1200 milli Jiao/square centimeter intensity, wavelength is that the ultraviolet light of 360 nanometers shines from transparent surface in the place of 50 centimetres of distance base materials and finished UV curing in 80 seconds, formation thickness is 20 microns antibiotic finishing coat on base material, promptly obtains antimicrobial coating material S3.
Comparative Examples 1
This Comparative Examples is used to illustrate existing antibacterial agent, antimicrobial coating composition and antimicrobial coating material.
Prepare antibacterial agent B1, antimicrobial coating composition and antimicrobial coating material C S1 with the method identical with embodiment 3, different is to replace the complex antimicrobials A3 of embodiment 1 with inorganic antiseptic (mixtures of 10 gram silver citrates, 5 gram zinc oxide and 5 gram copper nitrates).
Comparative Examples 2
This Comparative Examples is used to illustrate existing antibacterial agent, antimicrobial coating composition and antimicrobial coating material.
Prepare antibacterial agent B2, antimicrobial coating composition and antimicrobial coating material C S2 with the method identical with embodiment 3, different is to replace the complex antimicrobials A3 of embodiment 1 with organic antibacterial agent (mixtures of 7.5 gram isothiazolinone and 2.5 gram benzisothiazole ketone).
Comparative Examples 3
This Comparative Examples is used to illustrate existing complex antimicrobials, antimicrobial coating composition and antimicrobial coating material.
Prepare complex antimicrobials A3, antimicrobial coating composition and antimicrobial coating material C S3 respectively with the method identical with embodiment 3, different is, during the preparation complex antimicrobials, with complex antimicrobials (0.005 mole La
2O
3, 0.02 mole glutamic acid and 0.02 mole the mixture of imidazoles) replace the complex antimicrobials A3 of embodiment 3.
Embodiment 4
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare complex antimicrobials A4, antimicrobial coating composition and antimicrobial coating material S4 respectively according to the method identical with embodiment 1, different is, during the preparation complex antimicrobials, replace 7.5 gram isothiazolinone and 2.5 gram benzisothiazole ketone as organic antibacterial agent with 10 gram pyridines.
Embodiment 5
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare complex antimicrobials A5, antimicrobial coating composition and antimicrobial coating material S5 respectively according to the method identical with embodiment 1, different is during the preparation antimicrobial coating composition, to replace 8 to restrain vinyl silane triisopropoxides with 8 gram ethyl orthosilicates.
Embodiment 6
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare complex antimicrobials A6, antimicrobial coating composition and antimicrobial coating material S6 respectively according to the method identical with embodiment 1, different is during the preparation antimicrobial coating composition, to replace 2.5 to restrain 2, the 4-pentanedione with 2.5 gram ethyl acetoacetates.
Embodiment 7
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare complex antimicrobials A7, antimicrobial coating composition and antimicrobial coating material S7 respectively according to the method identical with embodiment 1, different is during the preparation antimicrobial coating composition, to replace 67 to restrain ethanol with 67 gram isopropyl alcohols.
Embodiment 8
Present embodiment is used to illustrate complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare complex antimicrobials A8, antimicrobial coating composition and antimicrobial coating material S8 respectively according to the method identical with embodiment 1, different is during the preparation antimicrobial coating composition, to replace 2 to restrain citric acids with 2 gram acetate.
Embodiment 9-12
Present embodiment is used to illustrate the anti-microbial property of complex antimicrobials provided by the invention.
The anti-microbial property of antimicrobial coating material is represented with antibiotic rate.With People's Republic of China's light industry standard standard No. is the method antibiotic rate of the complex antimicrobials A1-A4 of test implementation example 1-4 preparation respectively of QB/T 2591-2003, wherein need respectively complex antimicrobials A1-A4 to be diluted with water to 10 weight %, 0.2 weight, 0.03 weight %, 10 weight %, used bacterial classification is Escherichia coli (8099), staphylococcus aureus (ATCC6538).Test result when used bacterial classification is Escherichia coli (8099) is as shown in table 1 below, and the test result when used bacterial classification is staphylococcus aureus (ATCC6538) is as shown in table 2 below.
Comparative Examples 4-6
This Comparative Examples is used to illustrate the anti-microbial property of existing antibacterial agent.
Distinguish the antibiotic rate of the antibacterial agent B1-B3 of test comparison example 1-3 preparation with the method described in the embodiment 9-12, wherein need respectively antibacterial agent B1-B3 to be diluted with water to 0.03 weight %, 0.03 weight, 0.03 weight %, used bacterial classification is Escherichia coli (8099), staphylococcus aureus (ATCC6538).Test result when used bacterial classification is Escherichia coli (8099) is as shown in table 1 below, and the test result when used bacterial classification is staphylococcus aureus (ATCC6538) is as shown in table 2 below.
Table 1
| Antibacterial agent | The concentration of antibacterial agent (weight %) | Average clump count after 24 hours on the blank sample (cfu/ sheet) | Average clump count after 24 hours on the antimicrobial coating material (cfu/ sheet) | Antibiotic rate (%) | |
| Embodiment 9 | A1 | 10 | 2.3×10 5 | ＜1 | ＞99.99 |
| Embodiment 10 | A2 | 0.2 | 6.5×10 5 | 120 | 99.98 |
| Embodiment 11 | A3 | 0.03 | 4.0×10 5 | 1.9×10 4 | 95.25 |
| Comparative Examples 4 | B1 | 0.03 | 3.1×10 5 | 2.2×10 4 | 92.90 |
| Comparative Examples 5 | B2 | 0.03 | 6.0×10 5 | 4.9×10 4 | 91.83 |
| Comparative Examples 6 | B3 | 0.03 | 3.9×10 5 | 3.6×10 4 | 90.77 |
| Embodiment 12 | A4 | 10 | 2.5×10 5 | 18 | 99.99 |
Table 2
| Antibacterial agent | The concentration of antibacterial agent (weight %) | Average clump count after 24 hours on the blank sample (cfu/ sheet) | Average clump count after 24 hours on the antimicrobial coating material (cfu/ sheet) | Antibiotic rate (%) | |
| Embodiment 9 | A1 | 10 | 1.0×10 6 | 100 | 99.99 |
| Embodiment 10 | A2 | 0.2 | 1.5×10 6 | 1.3×10 4 | 99.13 |
| Embodiment 11 | A3 | 0.03 | 1.2×10 6 | 7.3×10 4 | 93.92 |
| Comparative Examples 4 | B1 | 0.03 | 1.1×10 6 | 1.2×10 5 | 89.09 |
| Comparative Examples 5 | B2 | 0.03 | 1.6×10 6 | 2.3×10 5 | 85.62 |
| Comparative Examples 6 | B3 | 0.03 | 1.2×10 6 | 1.8×10 5 | 85.00 |
| Embodiment 12 | A4 | 10 | 1.1×10 6 | 4.2×10 3 | 99.62 |
From the data of above-mentioned table 1 as can be seen, the anticolibacillary antibiotic rate during 0.03 weight % concentration of single antibacterial agent is 91.83-92.90%, will prepare RE (A) among the CN 101120681A
c(B)
dNH
2Anticolibacillary antibiotic rate when the raw material of O mixes as 0.03 weight % concentration of complex antimicrobials is 90.77%, and the anticolibacillary antibiotic rate during 0.03 weight % concentration of complex antimicrobials provided by the invention is 95.25%;
From the data of above-mentioned table 2 as can be seen, the antibiotic rate of the anti-staphylococcus aureus during 0.03 weight % concentration of single antibacterial agent is 85.62-89.09%, will prepare RE (A) among the CN 101120681A
c(B)
dNH
2The antibiotic rate of anti-staphylococcus aureus when the raw material of O mixes as 0.03 weight % concentration of complex antimicrobials is 85.00%, and the antibiotic rate of the anti-staphylococcus aureus during 0.03 weight % concentration of complex antimicrobials provided by the invention is 93.92%;
Illustrated and to have prepared RE (A) among the CN 101120681A
c(B)
dNH
2The raw material of O is about to rare earth ion, amino acid and azole heterocyclic compound and simply mixes, and can not produce synergy, and complex antimicrobials provided by the invention can produce synergy.
Embodiment 13-20
Present embodiment is used to illustrate the anti-microbial property of antimicrobial coating material provided by the invention.
Distinguish the antibiotic rate of the antimicrobial coating material S1-S8 of test implementation example 1-8 preparation with the method described in the embodiment 9-12, test result when used bacterial classification is Escherichia coli (8099) is as shown in table 3 below, and the test result when used bacterial classification is staphylococcus aureus (ATCC6538) is as shown in table 4 below.
Comparative Examples 7-9
This Comparative Examples is used to illustrate the anti-microbial property of existing antimicrobial coating material.
Distinguish the antibiotic rate of the antimicrobial coating material C S1-CS3 of test comparison example 1-3 preparation with the method described in the embodiment 9-12, test result when used bacterial classification is Escherichia coli (8099) is as shown in table 3 below, and the test result when used bacterial classification is staphylococcus aureus (ATCC6538) is as shown in table 4 below.
Table 3
| The antimicrobial coating material | The concentration of antibacterial agent (weight %) in the composition | Average clump count after 24 hours on the blank sample (cfu/ sheet) | Average clump count after 24 hours on the antimicrobial coating material (cfu/ sheet) | Antibiotic rate (%) | |
| Embodiment 13 | S1 | 10 | 2.5×10 5 | 280 | 99.89 |
| Embodiment 14 | S2 | 0.2 | 5.8×10 5 | 7.8×10 3 | 98.66 |
| Embodiment 15 | S3 | 0.03 | 3.7×10 5 | 2.9×10 4 | 92.16 |
| Comparative Examples 4 | CS1 | 0.03 | 3.2×10 5 | 4.7×10 4 | 85.31 |
| Comparative Examples 5 | CS2 | 0.03 | 5.6×10 5 | 9.7×10 4 | 82.68 |
| Comparative Examples 6 | CS3 | 0.03 | 3.5×10 5 | 5.3×10 4 | 84.86 |
| Embodiment 16 | S4 | 10 | 3.1×10 5 | 730 | 99.76 |
| Embodiment 17 | S5 | 10 | 2.9×10 5 | 850 | 99.71 |
| Embodiment 18 | S6 | 10 | 3.0×10 5 | 480 | 99.84 |
| Embodiment 19 | S7 | 10 | 3.1×10 5 | 2.6×10 3 | 99.16 |
| Embodiment 20 | S8 | 10 | 3.3×10 5 | 3.5×10 3 | 98.94 |
Table 4
| The antimicrobial coating material | The concentration of antibacterial agent (weight %) in the composition | Average clump count after 24 hours on the blank sample (cfu/ sheet) | Average clump count after 24 hours on the antimicrobial coating material (cfu/ sheet) | Antibiotic rate (%) | |
| Embodiment 13 | S1 | 10 | 1.1×10 6 | 2.3×10 3 | 99.79 |
| Embodiment 14 | S2 | 0.2 | 1.4×10 6 | 5.3×10 4 | 96.21 |
| Embodiment 15 | S3 | 0.03 | 1.2×10 6 | 1.3×10 5 | 89.17 |
| Comparative Examples 4 | CS1 | 0.03 | 1.0×10 6 | 1.6×10 5 | 84.00 |
| Comparative Examples 5 | CS2 | 0.03 | 1.5×10 6 | 2.8×10 5 | 81.33 |
| Comparative Examples 6 | CS3 | 0.03 | 1.2×10 6 | 2.0×10 5 | 83.33 |
| Embodiment 16 | S4 | 10 | 1.1×10 6 | 4.4×10 3 | 99.60 |
| Embodiment 17 | S5 | 10 | 1.0×10 6 | 4.3×10 3 | 99.57 |
| Embodiment 18 | S6 | 10 | 1.0×10 6 | 4.1×10 3 | 99.59 |
| Embodiment 19 | S7 | 10 | 1.1×10 6 | 1.2×10 4 | 98.90 |
| Embodiment 20 | S8 | 10 | 1.2×10 6 | 2.1×10 4 | 98.25 |
From the data of above-mentioned table 3 as can be seen, the anticolibacillary antibiotic rate when adopting the 0.03 weight % concentration of the antimicrobial coating material C S1 of single antibacterial agent and CS2 is 82.68-85.31%, will prepare RE (A) among the CN101120681A
c(B)
dNH
2Anticolibacillary antibiotic rate when the raw material of O mixes as the 0.03 weight % concentration of the antimicrobial coating material C S3 of complex antimicrobials is 84.86%, and the anticolibacillary antibiotic rate during the 0.03 weight % concentration of antimicrobial coating material S1-S3 provided by the invention is 92.16%;
From the data of above-mentioned table 4 as can be seen, the antibiotic rate of the anti-staphylococcus aureus when adopting the 0.03 weight % concentration of the antimicrobial coating material C S1 of single antibacterial agent and CS2 is 81.33-84.00%, will prepare RE (A) among the CN 101120681A
c(B)
dNH
2The antibiotic rate of anti-staphylococcus aureus when the raw material of O mixes as the 0.03 weight % concentration of the antimicrobial coating material C S3 of complex antimicrobials is 83.33%, and the antibiotic rate of the anti-staphylococcus aureus during the 0.03 weight % concentration of antimicrobial coating material S1-S3 provided by the invention is 89.17%;
Illustrated and to have prepared RE (A) among the CN 101120681A
c(B)
dNH
2The raw material of O is about to rare earth ion, amino acid and azole heterocyclic compound and simply mixes, and can not produce synergy, and complex antimicrobials provided by the invention can produce synergy.
Claims (15)
1, a kind of complex antimicrobials, this complex antimicrobials contains inorganic antiseptic and organic antibacterial agent, it is characterized in that, described inorganic antiseptic is slaine and/or the metal oxide with antibacterial activity, and described organic antibacterial agent is for having shown in following formula (I) and/or the formula (II) compound formed and in the pyridine one or more:
R
1And R
2Respectively do for oneself hydrogen or carbon number is the alkyl of 1-8.
2, complex antimicrobials according to claim 1, wherein, the weight ratio of described inorganic antiseptic and organic antibacterial agent is 0.5-5: 1.
3, complex antimicrobials according to claim 1 and 2, wherein, described organic antibacterial agent is one or more in isothiazolinone, benzisothiazole ketone and the pyridine.
4, complex antimicrobials according to claim 3, wherein, described organic antibacterial agent is the mixture of isothiazolinone and benzisothiazole ketone, the weight ratio of isothiazolinone and benzisothiazole ketone is 1-5: 1.
5, complex antimicrobials according to claim 1 and 2, wherein, described inorganic antiseptic is one or more slaine and/or the metal oxide in silver, zinc, copper, lanthanum, cerium, praseodymium, neodymium, erbium, europium, yttrium, dysprosium and the gadolinium.
6, complex antimicrobials according to claim 5, wherein, described inorganic antiseptic is one or more in silver salt, silver oxide, zinc salt, zinc oxide, mantoquita and the copper oxide.
7, complex antimicrobials according to claim 6, wherein, described silver salt, zinc salt and mantoquita respectively do for oneself citrate and/or nitrate.
8, a kind of antimicrobial coating composition, said composition contains organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid, antibacterial agent, curing agent and thinner, and curing agent does not coexist with other component, described organic complexing agent is the compound that contains two or more carbonyls, described polar organic solvent is that carbon number is the alcohol of 2-4, it is characterized in that described antibacterial agent is any described complex antimicrobials among the claim 1-7.
9, antimicrobial coating composition according to claim 8, wherein, gross weight with composition is a benchmark, the content of described organosilicon and organic titanium is 8-9 weight %, the content of described organic complexing agent is 2.5-3 weight %, the content of described polar organic solvent is 52.8-70 weight %, described inorganic acid and organic acid content are 2-3 weight %, the content of described complex antimicrobials is 0.03-10 weight %, the content of described curing agent is 0.3-2 weight %, and the content of described thinner is 10-30 weight %.
10, according to Claim 8 or 9 described antimicrobial coating compositions, wherein, under non-working condition, curing agent independently exists.
11, according to Claim 8 or 9 described antimicrobial coating compositions, wherein, described organosilicon is one or more in ethyl orthosilicate, positive isopropyl silicate, vinyl silane triisopropoxide and the vinyltrimethoxy silane, and described organic titanium is one or more in tetraethyl titanate, isopropyl titanate and the tetrabutyl titanate; Described organic complexing agent is 2, one or more in 4-pentanedione, hydroresorcinol and the ethyl acetoacetate; Described polar organic solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol and the n-butanol; Described inorganic acid is one or more in hydrochloric acid, sulfuric acid and the nitric acid, and described organic acid is one or more in acetate, citric acid and the tartaric acid; Described curing agent is dibutyl tin laurate, ammonium acetate, 2, one or more in the 4-diamino benzene sulfonic acid sodium and 2, and the mixture of 4-toluene di-isocyanate(TDI), wherein, in this mixture 2, the content of 4-toluene di-isocyanate(TDI) is 90-95 weight %; Described thinner is 1-Methoxy-2-propyl acetate and/or butyl acetate.
12, antimicrobial coating composition according to claim 11, wherein, described organosilicon is a vinyl silane triisopropoxide, described organic titanium is a tetrabutyl titanate, described organic complexing agent is 2, and 4-pentanedione, described polar organic solvent are ethanol, described inorganic acid is a nitric acid, and described organic acid is a citric acid.
13, a kind of antimicrobial coating material, this material comprises base material and is positioned at the antibiotic finishing coat of substrate surface, this antibiotic finishing coat obtains after being solidified by a kind of antimicrobial coating composition, it is characterized in that described antimicrobial coating composition is any described antimicrobial coating composition among the claim 8-12.
14, antimicrobial coating material according to claim 13, wherein, the thickness of described antibiotic finishing coat is the 15-25 micron.
15, antimicrobial coating material according to claim 13, wherein, described base material is acrylonitrile/butadiene/styrene copolymer, polypropylene, Merlon and their complex, or stainless steel, titanium, magnesium, aluminium, zinc and their alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101106173A CN101595880B (en) | 2008-06-06 | 2008-06-06 | Compound antimicrobial agent, antimicrobial coating composition and antimicrobial coating materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101106173A CN101595880B (en) | 2008-06-06 | 2008-06-06 | Compound antimicrobial agent, antimicrobial coating composition and antimicrobial coating materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101595880A true CN101595880A (en) | 2009-12-09 |
| CN101595880B CN101595880B (en) | 2013-12-04 |
Family
ID=41417621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101106173A Expired - Fee Related CN101595880B (en) | 2008-06-06 | 2008-06-06 | Compound antimicrobial agent, antimicrobial coating composition and antimicrobial coating materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101595880B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265540A (en) * | 2013-04-13 | 2013-08-28 | 李美凤 | Active isothiazolinone antibiotic finishing agent |
| CN103459512A (en) * | 2011-02-15 | 2013-12-18 | 东洋制罐集团控股株式会社 | Antibacterial resin composition |
| CN103694761A (en) * | 2013-12-05 | 2014-04-02 | 江苏金波新材料科技有限公司 | Anti-bacterial coating for pipeline and preparation method thereof |
| CN103740155A (en) * | 2013-12-05 | 2014-04-23 | 江苏金波新材料科技有限公司 | Antibacterial pipeline |
| CN104403458A (en) * | 2014-12-18 | 2015-03-11 | 常熟市亨利医疗器械有限公司 | Medical nail dismantling pincers |
| CN106752587A (en) * | 2016-12-26 | 2017-05-31 | 广西宾阳县荣良新材料科技有限公司 | A kind of kitchen wall surface fireproof mould-proof coating and its production method |
| CN107163322A (en) * | 2017-06-14 | 2017-09-15 | 合肥易美特建材有限公司 | A kind of rubber floor covering |
| CN107205374A (en) * | 2015-02-03 | 2017-09-26 | 狮王株式会社 | The living space inorganic agent of piezoelectric type sprayer |
| CN107245281A (en) * | 2017-07-26 | 2017-10-13 | 炫杰复合材料（上海）有限公司 | Oneself sterilizing interior wall coating of a kind of copper ion and preparation method thereof |
| CN107619619A (en) * | 2017-09-06 | 2018-01-23 | 湖北睿智新材料有限责任公司 | A kind of brilliant swimming powdery paints of extra-weather-proof antibacterial |
| CN109096727A (en) * | 2018-08-28 | 2018-12-28 | 安徽江淮汽车集团股份有限公司 | A kind of imitative metal appearance antibacterial PC composite material |
| CN109704578A (en) * | 2019-02-18 | 2019-05-03 | 青田县南方陶瓷原料有限公司 | A kind of antibacterial ceramic glaze and preparation method thereof that glaze is clear |
| CN110845888A (en) * | 2019-10-26 | 2020-02-28 | 宁波维楷化学有限公司 | Preparation method of nano composite antibacterial agent for powder coating |
| CN111269212A (en) * | 2020-04-01 | 2020-06-12 | 深圳市康益保健用品有限公司 | Antimicrobial metal complex, application method and product prepared by using antimicrobial metal complex |
| CN111606577A (en) * | 2020-05-29 | 2020-09-01 | 北京崇高纳米科技有限公司 | Antibacterial tempered glass film and preparation method thereof |
| CN114146887A (en) * | 2021-12-08 | 2022-03-08 | 广德竹昌电子科技有限公司 | Antibacterial and antiviral treatment process for workpiece |
| CN115119850A (en) * | 2022-07-11 | 2022-09-30 | 浙江新安化工集团股份有限公司 | Compound mildew-proof antibacterial agent, preparation method thereof, long-acting mildew-proof alcohol-type sealant and preparation method thereof |
| CN115417828A (en) * | 2022-07-12 | 2022-12-02 | 广东天龙油墨有限公司 | Antibacterial environment-friendly acrylic acid material and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102021117979A1 (en) * | 2021-07-12 | 2023-01-12 | Daxem GmbH | coating composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1880368A (en) * | 2005-06-15 | 2006-12-20 | 乐金电子(天津)电器有限公司 | Antibiotic plastic and barrel washing machine erecting bed produced using same |
| US9723842B2 (en) * | 2006-05-26 | 2017-08-08 | Arch Chemicals, Inc. | Isothiazolinone biocides enhanced by zinc ions |
-
2008
- 2008-06-06 CN CN2008101106173A patent/CN101595880B/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103459512B (en) * | 2011-02-15 | 2016-08-10 | 东洋制罐集团控股株式会社 | Antibacterial resin composition |
| CN103459512A (en) * | 2011-02-15 | 2013-12-18 | 东洋制罐集团控股株式会社 | Antibacterial resin composition |
| CN103265540A (en) * | 2013-04-13 | 2013-08-28 | 李美凤 | Active isothiazolinone antibiotic finishing agent |
| CN103740155B (en) * | 2013-12-05 | 2016-08-17 | 江苏金波新材料科技有限公司 | A kind of pipeline with antibacterial action |
| CN103740155A (en) * | 2013-12-05 | 2014-04-23 | 江苏金波新材料科技有限公司 | Antibacterial pipeline |
| CN103694761A (en) * | 2013-12-05 | 2014-04-02 | 江苏金波新材料科技有限公司 | Anti-bacterial coating for pipeline and preparation method thereof |
| CN104403458A (en) * | 2014-12-18 | 2015-03-11 | 常熟市亨利医疗器械有限公司 | Medical nail dismantling pincers |
| CN107205374A (en) * | 2015-02-03 | 2017-09-26 | 狮王株式会社 | The living space inorganic agent of piezoelectric type sprayer |
| CN106752587A (en) * | 2016-12-26 | 2017-05-31 | 广西宾阳县荣良新材料科技有限公司 | A kind of kitchen wall surface fireproof mould-proof coating and its production method |
| CN106752587B (en) * | 2016-12-26 | 2019-03-29 | 广西宾阳县荣良新材料科技有限公司 | A kind of kitchen wall surface fireproof mould-proof coating and its production method |
| CN107163322A (en) * | 2017-06-14 | 2017-09-15 | 合肥易美特建材有限公司 | A kind of rubber floor covering |
| CN107245281B (en) * | 2017-07-26 | 2019-05-31 | 炫杰复合材料（上海）有限公司 | A kind of copper ion is from sterilizing interior wall coating and preparation method thereof |
| CN107245281A (en) * | 2017-07-26 | 2017-10-13 | 炫杰复合材料（上海）有限公司 | Oneself sterilizing interior wall coating of a kind of copper ion and preparation method thereof |
| CN107619619A (en) * | 2017-09-06 | 2018-01-23 | 湖北睿智新材料有限责任公司 | A kind of brilliant swimming powdery paints of extra-weather-proof antibacterial |
| CN109096727A (en) * | 2018-08-28 | 2018-12-28 | 安徽江淮汽车集团股份有限公司 | A kind of imitative metal appearance antibacterial PC composite material |
| CN109704578A (en) * | 2019-02-18 | 2019-05-03 | 青田县南方陶瓷原料有限公司 | A kind of antibacterial ceramic glaze and preparation method thereof that glaze is clear |
| CN109704578B (en) * | 2019-02-18 | 2021-12-07 | 青田县南方玻纤原料有限公司 | Antibacterial ceramic glaze with clear glaze surface and preparation method thereof |
| CN110845888A (en) * | 2019-10-26 | 2020-02-28 | 宁波维楷化学有限公司 | Preparation method of nano composite antibacterial agent for powder coating |
| CN111269212A (en) * | 2020-04-01 | 2020-06-12 | 深圳市康益保健用品有限公司 | Antimicrobial metal complex, application method and product prepared by using antimicrobial metal complex |
| CN111606577A (en) * | 2020-05-29 | 2020-09-01 | 北京崇高纳米科技有限公司 | Antibacterial tempered glass film and preparation method thereof |
| CN111606577B (en) * | 2020-05-29 | 2023-02-21 | 北京崇高纳米科技有限公司 | Antibacterial tempered glass film and preparation method thereof |
| CN114146887A (en) * | 2021-12-08 | 2022-03-08 | 广德竹昌电子科技有限公司 | Antibacterial and antiviral treatment process for workpiece |
| CN115119850A (en) * | 2022-07-11 | 2022-09-30 | 浙江新安化工集团股份有限公司 | Compound mildew-proof antibacterial agent, preparation method thereof, long-acting mildew-proof alcohol-type sealant and preparation method thereof |
| CN115417828A (en) * | 2022-07-12 | 2022-12-02 | 广东天龙油墨有限公司 | Antibacterial environment-friendly acrylic acid material and preparation method and application thereof |
| CN115417828B (en) * | 2022-07-12 | 2024-02-27 | 广东天龙油墨有限公司 | Antibacterial environment-friendly acrylic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101595880B (en) | 2013-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101595880B (en) | Compound antimicrobial agent, antimicrobial coating composition and antimicrobial coating materials | |
| US9011890B2 (en) | Antibacterial sol-gel coating solution | |
| CN100503753C (en) | Nano antibacterial aqueous woodenware paint and preparing method thereof | |
| CN105494429B (en) | Antibacterial mildew preventive, preparation method thereof and antibacterial mildew preventive method | |
| US8647652B2 (en) | Stable silver colloids and silica-coated silver colloids, and methods of preparing stable silver colloids and silica-coated silver colloids | |
| RU2647086C2 (en) | Surface coating | |
| CN101921501B (en) | Nano coating additive and coating composition containing same | |
| CN103271048B (en) | Antibacterial composition containing organic silver complexes, antibacterial treatment methods using the same and antibacterial formed article | |
| CN107469820A (en) | A kind of photocatalyst and preparation method thereof | |
| CN103468096A (en) | Environmental protection type long-acting anti-mildew coating material preparation method | |
| CN106000423B (en) | TiO2/MnS/Ga2O3Composite photocatalyst colloid preparation method | |
| EP1885912B1 (en) | Method for improving corrosion resistance of metal surfaces | |
| CN1704403A (en) | Nano rare earth m-hydroxy benzoic acid 8-hydroxyquinoline antibacterial agent and method for preparing same | |
| KR20040084571A (en) | Functional acrylic water paint that radiating an anion and a far infrared rays | |
| CN1328170C (en) | Silver face finished nano zinc oxide and preparation method | |
| CN101103732A (en) | Strong effect wide-spectrum antibacterial liquid | |
| CN114318948B (en) | Antibacterial impregnated paper and preparation method and application thereof | |
| CN105017896A (en) | Antibacterial finishing coat for wood products | |
| CN104130689B (en) | Metal exterior wall paint and preparation method thereof | |
| CN109836952A (en) | A kind of woodwork Antibacterial finish paint | |
| KR100524050B1 (en) | Antifouling coating composition and a method for manufacturing thereof | |
| CN105462308A (en) | Antibacterial anti-fingerprint multi-performance synergistic agentia and preparation method thereof | |
| CN104371381A (en) | Antibiotic aluminum pigment and preparation method thereof | |
| CN114541033B (en) | Monoatomic antibacterial antiviral mildew-proof aldehyde-removing non-woven fabric and preparation method thereof | |
| CN113615711B (en) | Long-acting microorganism protection composition and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131204 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |