CN101595880B - Compound antimicrobial agent, antimicrobial coating composition and antimicrobial coating materials - Google Patents
Compound antimicrobial agent, antimicrobial coating composition and antimicrobial coating materials Download PDFInfo
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Abstract
The invention provides a compound antimicrobial agent containing an inorganic antimicrobial agent and an organic antimicrobial agent, wherein the inorganic antimicrobial agent is metal salt and/or metallic oxides with antimicrobial activity; the organic antimicrobial agent is a composition the formation of which is shown in an above formula (I) and/or formula (II) and is one or several of pyridines, wherein R1 and R2 showed in the formula (I) and the formula (II) are alkyls with the number of hydrogen atoms or carbon atoms from 1 to 8. The invention also provides an antimicrobial coating composition containing the compound antimicrobial agent and antimicrobial coating materials using the antimicrobial coating composition. The compound antimicrobial agent is prepared by a very simple method and can achieve the very favorable antimicrobial effect by only simply mixing the inorganic antimicrobial agent and the organic antimicrobial agent of the compound antimicrobial 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 composition that contains this complex antimicrobials and the antimicrobial coating material that has used this antimicrobial coating composition.
Background technology
Along with improving constantly of social development and living standards of the people, people have higher requirement to 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 not only can cause that the burn into of material decomposes, the health that is also threatening the mankind.Thereby the antimicrobial product that can ensure to some extent health more and more is subject to people's favor.
And the core of antimicrobial product is the development of antibacterial agent, common antibacterial agent has inorganic antiseptic, organic antibacterial agent.The advantage such as that inorganic antiseptic has is safe, good heat resistance, persistence are good, but there is the shortcoming of antibiotic late effect property; High but the poor durability of the general short-term antibiotic property of organic antibacterial agent.As can be seen here, above-mentioned single type antibacterial agent is difficult to meet the existing market demand, thereby realizes that spectrum truly is antibiotic.Therefore, the complex antimicrobials of development of new just more and more receives people's concern.
At present, people have recognized the compound tense carried out between different antibacterial agents, need to make complex antimicrobials produce synergy, synergy between 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 preparation method and application, the chemical formula of described nanometer inorganic-organic composite antibiotic material is 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 comprises the following steps:
1) in the nonaqueous solvents at 40-80 ℃ of temperature, according to rare earth ion: the ratio that amino acid molar ratio is 1: 2 to 1: 4 feed intake and by the two return stirring to sufficient reacting;
2) continue to add the alcoholic solution of the azole heterocyclic compound that is equivalent to rare earth ion 2-4 times mole, stir, adjust pH to 5-8, continue to stir;
3) by the solution decompression distillation, the bottoms of acquisition are fully washed with absolute ether and acetone, at 40-80 ℃ of lower vacuum drying 4-10 hour, obtain powdered product.
Although in above-mentioned patent documentation, disclosed complex antimicrobials can reach antibacterial effect preferably when lower content, its preparation technology is more complicated.
Summary of the invention
The object of the invention is to overcome the defect of existing complex antimicrobials complicated process of preparation, a kind of can simply make and can produce synergistic complex antimicrobials and the antimicrobial coating composition that contains this complex antimicrobials and the antimicrobial coating material that has used this antimicrobial coating composition are provided.
The invention provides a kind of by simple just mixing of different antibacterial agents can be produced to synergistic complex antimicrobials,, 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 formula (II) and one or more in pyridine:
R
1And R
2The alkyl that hydrogen or carbon number be 1-8 of respectively doing for oneself.
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 the alcohol that carbon number is 2-4, wherein, described antibacterial agent is 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 antimicrobial coating composition provided by the invention.
Complex antimicrobials provided by the invention, the preparation method is very simple, only need carry out simple mixing 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 to have the compound of composition shown in following formula (I) and/or formula (II) and one or more in pyridine:
R
1And R
2The alkyl that hydrogen or carbon number be 1-8 of respectively doing for oneself.
The example of the alkyl that described carbon number is 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.
Consider being easy to get property and the antibacterial activity of raw material, described organic antibacterial agent is preferably one or more in isothiazolinone, BIT and pyridine, more preferably the mixture of isothiazolinone and BIT.The present inventor finds, when the described organic antibacterial agent mixture that is isothiazolinone and BIT, and the weight ratio of the mixture of isothiazolinone and BIT 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%.So the present invention's composition that more preferably described organic antibacterial agent is isothiazolinone and BIT, the weight ratio of isothiazolinone and BIT 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, can be for example one or more slaine and/or the metal oxide in silver, zinc, copper, lanthanum, cerium, praseodymium, neodymium, erbium, europium, yttrium, dysprosium and gadolinium, preferred described inorganic antiseptic is one or more in silver salt, silver oxide, zinc salt, zinc oxide, mantoquita and 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 embodiment, 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 containing two or more carbonyls, described polar organic solvent is the alcohol that carbon number is 2-4, wherein, described antibacterial agent is complex antimicrobials provided by the invention.
The present invention has no particular limits the content of complex antimicrobials in described composition, and the gross weight of composition of take is benchmark, and the content of complex antimicrobials can be the 0.03-10 % by weight.Experiment showed, under the certain condition of the content of the complex antimicrobials in antibiotic finishing coat, when the thickness of antibiotic finishing coat is the 15-25 micron, the antibiotic rate of antimicrobial coating material does not change with the variation of the thickness of antibiotic finishing coat.When therefore the thickness of the antibiotic finishing coat after described composition applies and solidifies is the 15-25 micron, in described composition, the content of complex antimicrobials can be the 0.03-10 % by weight, is preferably the 0.03-0.2 % by weight; When in described composition, the content of complex antimicrobials is the 0.03-0.2 % by 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 during higher than 0.2 % by weight, raising along with the content of complex antimicrobials, antibiotic rate can increase, but effect not obvious, simultaneously, along with the raising of the content of complex antimicrobials, its cost also correspondingly improves, therefore, from the economy aspect, consider, in described composition, the content of complex antimicrobials is preferably the 0.03-0.2 % by weight.In addition, the gross weight of composition of take is benchmark, the content of organosilicon described in composition and organic titanium is the 8-9 % by weight, the content of described organic complexing agent is the 2.5-3 % by weight, the content of described polar organic solvent is the 52.8-70 % by weight, described inorganic acid and organic acid content are the 2-3 % by weight, and the content of described curing agent is the 0.3-2 % by weight, and the content of described thinner is the 10-30 % by weight.
Preferred organosilicon in organosilicon and organic titanium, described organosilicon can be various esters of silicon acis, as long as have silicon-alkoxyl (Si-OR ', R ' is alkyl) structure gets final product, be specifically as follows one or more in ethyl orthosilicate, positive isopropyl silicate, vinyl silane triisopropoxide and vinyltrimethoxy silane, preferred vinyl three isopropoxy silane; Described organic titanium can be various titanate esters, as long as have titanium-alkoxyl (Ti-OR ', R ' is alkyl) structure, gets final product, and is specifically as follows one or more in tetraethyl titanate, isopropyl titanate and tetrabutyl titanate, preferably tetrabutyl titanate;
The alcohol that the preferred carbon number of described polar organic solvent is 2-4, the alcohol that described carbon number is 2-4 can be one or more in methyl alcohol, ethanol, isopropyl alcohol and n-butanol, preferred alcohol; Described organic complexing agent be for can be 2 containing two or more active carbonyl compounds, 4-pentanedione, 1, one or more in hydroresorcinol and ethyl acetoacetate, preferably 2,4-pentanedione;
Preferred organic acid in organic acid and inorganic acid, described inorganic acid can be one or more in hydrochloric acid, sulfuric acid and nitric acid, preferably nitric acid; Described organic acid can be one or more in acetic acid, citric acid and tartaric acid, optimization citric acid;
Described curing agent can for routine for making the curing curing agent of colloidal sol, can be for example dibutyl tin laurate, ammonium acetate, 2, one or more in 4-diamino benzene sulfonic acid sodium and 2, the mixture of 4-toluene di-isocyanate(TDI), wherein, in this mixture 2, the content of 4-toluene di-isocyanate(TDI) is the 90-95 % by weight, described thinner can for routine for regulating the viscosity of composition, controlling the solvent of wet film rate of drying, can be for example 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 described composition, flatting silica generally has delustring, transparent, thickening, anti-scratch flower and the effect easily disperseed, described flatting silica can be conventional flatting silica, the equally distributed micron that for example can make for the precipitation method or vapor phase method or one or more in nanometer grade silica, for example can be for being purchased from the Shanghai ACEMATT of the Hai Yi scientific & trading Co., Ltd. trade mark, the silica of the TS100 trade mark or the OK500 trade mark, the gross weight of composition of take is benchmark, the consumption of described flatting silica is the 0.2-5 % by weight.
According to the present invention, in described composition, curing agent can not coexist with other composition, because curing agent and other composition are while coexisting, between composition, curing reaction can occur.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 the 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 stable colloidal sol shape, before use, first in colloidal sol, add thinner to regulate the viscosity of colloidal sol, add again curing agent to 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 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 stable colloidal sol shape, before use, add curing agent to mix, and can apply.
Perhaps also can directly each component in composition be mixed to rear coating before use.
Preferred first two mode, described organosilicon and/or organic titanium, organic complexing agent, polar organic solvent, inorganic acid and/or organic acid and complex antimicrobials are present in the 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 same component, and curing agent is present in another component.The antibacterial effect of the antimicrobial coating composition of these preferred two kinds of modes 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 antimicrobial coating composition provided by the invention.
During use, described composition is got final product with being coated on base material after water mixes, described on base material the method for coating composition can be conventional coating method, for example can directly apply or spray, from the adhesive force aspect between composition and base material, consider, the method preferably sprayed, for example can be sprayed with spray gun, in addition, as those skilled in the known, particle in composition is less, and the adhesive force between composition and base material is better, therefore, preferably, before spraying, first composition is crossed to 500-600 purpose filter cloth.
The method that the described curing method of composition that will be coated on base material can be known to the skilled person, for example can be for heat cure or UV solidify, and heat cure can be baking 15-45 minute under 70-90 ℃; UV solidifies can be for ultraviolet light is irradiated to 30-120 second from antibiotic finishing coat surface, and the UV condition of cure comprises that the ultraviolet light intensity is 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, in order to make substrate surface, have certain resistance to marring, 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 preferable case, described antimicrobial coating material can also comprise between base material and antibiotic finishing coat, for the overlay that improves substrate surface and the adhesive force between base material priming coat, the thickness of described priming coat can be the 8-12 micron.Described priming coat can be the conventional overlay that can improve substrate surface and the coating of the adhesive force between base material, be conventionally known to one of skill in the art, can be generally the priming paint that contains the polyurethanes compound, for example can be for being purchased from the thermosetting paint of Akzo Nobel's coating SC-J-B14121 of Co., Ltd trade mark, or be purchased from the thermosetting paint of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark.
The present invention has no particular limits the method that forms priming coat on base material, can be conventional method, concrete identical with the method for coating composition on base material, do not repeat them here, difference is preferably, before spraying, first composition to be crossed to 300-400 purpose filter cloth.
As those skilled in the known, on base material, after the coating priming coat, need make priming coat solidify, described solidifying can be heat cure, and the method for described heat cure is conventional method, for example can under 70-90 ℃, toast 5-15 minute.
When the color to base material has requirement, described antimicrobial coating material can also comprise between priming coat and antibiotic finishing coat, for the floating coat of the color of regulating the antimicrobial coating material, and the thickness of described floating coat can be the 10-15 micron.Described floating coat can for the conventional color that can regulate substrate surface and improve priming coat and antibiotic finishing coat between the coating of adhesive force, be conventionally known to one of skill in the art, it can be generally the colored paint that contains the polyurethanes compound, for example can be for being purchased from the thermosetting paint of Akzo Nobel's coating SC-D-Z24072 of Co., Ltd trade mark, or be purchased from the thermosetting paint of the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark.Wherein, the thermosetting paint and the adhesive force between base material and antibiotic finishing coat that are purchased from the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark are all better, therefore when priming coat and floating coat are the thermosetting paint that is purchased from the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark, 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 conventional method, concrete identical with the method for coating composition on base material, do not repeat them here, difference is preferably, before spraying, first composition to be crossed to 400-500 purpose filter cloth.
As those skilled in the known, on priming coat, after the coating floating coat, need make floating coat solidify, described solidifying can be heat cure, and the method for described heat cure is conventional method, for example can under 70-90 ℃, toast 5-15 minute.
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.
Below adopt specific embodiment to be further elaborated to the present invention.
Embodiment 1
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
(1) prepare 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 BITs) are mixed, be complex antimicrobials A1 of the present invention.
(2) prepare antimicrobial coating composition
By the complex antimicrobials of the above-mentioned preparation of 10 gram, 8 gram vinyl silane triisopropoxides, 2.5 grams 2,4-pentanedione, 67 gram ethanol, 2 gram citric acids and 0.2 gram flatting silica (TS100 of Shanghai Hai Yi scientific & trading Co., Ltd.) mix, and are the colloidal sol shape.
In the colloidal sol of above-mentioned preparation, add 10 gram 1-Methoxy-2-propyl acetates to mix, then add 0.27 gram 2,4-toluene di-isocyanate(TDI), 0.03 gram dibutyl tin laurate mix and obtain composition.
(3) prepare the antimicrobial coating material
After the thermosetting paint that 20 grams are purchased to Akzo Nobel's coating SC-J-B14121 of Co., Ltd trade mark is crossed 300 order filter clothes, with spray gun, be sprayed onto on stainless steel substrate (the emerging stainless steel BS/SUS304-O of the Co., Ltd trade mark of Ningbo profit) surface, then 70 ℃ of bakings 15 minutes, form the priming coat that thickness is 10 microns on base material.
After the thermosetting paint that 25 grams are purchased to the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark is crossed 400 order filter clothes, with spray gun, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat, then 70 ℃ of bakings 15 minutes, form the floating coat that thickness is 12 microns on base material.
After the composition of the above-mentioned preparation of 50 gram is crossed to 500 order filter clothes, with spray gun, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with successively priming coat and floating coat, then 70 ℃ of bakings 45 minutes, form the antibiotic finishing coat that thickness is 25 microns on base material, obtain antimicrobial coating material S1.
Embodiment 2
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
(1) prepare complex antimicrobials
30 gram inorganic antiseptics (30 gram silver citrate) and 10 gram organic antibacterial agents (8 gram isothiazolinone and 2 gram BITs) are mixed, be complex antimicrobials A2 of the present invention.
(2) prepare antimicrobial coating composition
By the complex antimicrobials of the above-mentioned preparation of 0.2 gram, 9 gram ethyl orthosilicates, 3 grams 1, hydroresorcinol, 52.8 gram isopropyl alcohols, 3 gram tartaric acid and 30 gram butyl acetates mix, and are 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 obtain composition.
(3) prepare the antimicrobial coating material
After the thermosetting paint that 15 grams are purchased to the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark is crossed 400 order filter clothes, with spray gun, be sprayed onto on polycarbonate substrate (U.S. EXL1414 of the GE company trade mark) surface, then 80 ℃ of bakings 10 minutes, form the priming coat that thickness is 8 microns on base material.
After the thermosetting paint that 20 grams are purchased to the 3667-00050 of Shenzhen Pinefield Chemical Enterprises Co., Ltd. trade mark is crossed 500 order filter clothes, with spray gun, be sprayed onto on the above-mentioned polypropylene base surface that is formed with priming coat, then 80 ℃ of bakings 10 minutes, form the floating coat that thickness is 10 microns on base material.
After the composition of the above-mentioned preparation of 30 gram is crossed to 600 order filter clothes, with spray gun, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with successively priming coat and floating coat, then 90 ℃ of bakings 15 minutes, form the antibiotic finishing coat that thickness is 15 microns on base material, obtain antimicrobial coating material S2.
Embodiment 3
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
(1) prepare 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 BITs) are mixed, be complex antimicrobials A3 of the present invention.
(2) prepare antimicrobial coating composition
By the complex antimicrobials of the above-mentioned preparation of 0.03 gram, the positive isopropyl silicate of 8.5 gram, 2.8 gram ethyl acetoacetates, 60.17 gram n-butanols, 2.5 gram nitric acid, 5 gram flatting silicas (OK500 of Shanghai Hai Yi scientific & trading Co., Ltd.), 0.92 gram 2,4-toluene di-isocyanate(TDI), 0.08 gram 2,4-diamino benzene sulfonic acid sodium and 20 gram butyl acetates mix, and obtain composition.
(3) prepare the antimicrobial coating material
After the thermosetting paint that 25 grams are purchased to Akzo Nobel's coating SC-J-B14121 of Co., Ltd trade mark is crossed 300 order filter clothes, with spray gun, be sprayed onto on the magnesium substrates surface, then 90 ℃ of bakings 15 minutes, form the priming coat that thickness is 12 microns on base material.
After the thermosetting paint that 30 grams are purchased to Akzo Nobel's coating SC-D-Z24072 of Co., Ltd trade mark is crossed 400 order filter clothes, with spray gun, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with priming coat, then 90 ℃ of bakings 15 minutes, form the floating coat that thickness is 15 microns on base material.
After the composition of the above-mentioned preparation of 40 gram is crossed to 500 order filter clothes, with spray gun, be sprayed onto on the above-mentioned stainless steel substrate surface that is formed with successively priming coat and floating coat, then with 1200 millis burnt/square centimeter is intensity, ultraviolet light that wavelength is 360 nanometers is irradiated and within 80 seconds, completes UV and solidify from transparent surface in the place of 50 centimetres of distance base materials, form the antibiotic finishing coat that thickness is 20 microns on base material, obtain antimicrobial coating material S3.
Comparative Examples 1
This Comparative Examples is for illustrating existing antibacterial agent, antimicrobial coating composition and antimicrobial coating material.
Prepare antibacterial agent B1, antimicrobial coating composition and antimicrobial coating material C S1 by the method identical with embodiment 3, different, with the complex antimicrobials A3 of inorganic antiseptic (mixtures of 10 gram silver citrates, 5 gram zinc oxide and 5 gram copper nitrates) replacement embodiment 1.
Comparative Examples 2
This Comparative Examples is for illustrating existing antibacterial agent, antimicrobial coating composition and antimicrobial coating material.
Prepare antibacterial agent B2, antimicrobial coating composition and antimicrobial coating material C S2 by the method identical with embodiment 3, different, with the complex antimicrobials A3 of organic antibacterial agent (mixtures of 7.5 gram isothiazolinone and 2.5 gram BITs) replacement embodiment 1.
Comparative Examples 3
This Comparative Examples is for illustrating existing complex antimicrobials, antimicrobial coating composition and antimicrobial coating material.
Prepare respectively complex antimicrobials A3, antimicrobial coating composition and antimicrobial coating material C S3 by the method identical with embodiment 3, different, while preparing complex antimicrobials, with the complex antimicrobials (La of 0.005 mole
2O
3, the glutamic acid of 0.02 mole and 0.02 mole the mixture of imidazoles) replace the complex antimicrobials A3 of embodiment 3.
Embodiment 4
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare respectively complex antimicrobials A4, antimicrobial coating composition and antimicrobial coating material S4 according to the method identical with embodiment 1, different is, while preparing complex antimicrobials, with 10 gram pyridines, replace 7.5 gram isothiazolinone and 2.5 gram BITs as organic antibacterial agent.
Embodiment 5
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare respectively complex antimicrobials A5, antimicrobial coating composition and antimicrobial coating material S5 according to the method identical with embodiment 1, different, while preparing antimicrobial coating composition, with 8 gram ethyl orthosilicates, replace 8 gram vinyl silane triisopropoxides.
Embodiment 6
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare respectively complex antimicrobials A6, antimicrobial coating composition and antimicrobial coating material S6 according to the method identical with embodiment 1, different, while preparing antimicrobial coating composition, with 2.5 gram ethyl acetoacetates, replace 2.5 grams 2,4-pentanedione.
Embodiment 7
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare respectively complex antimicrobials A7, antimicrobial coating composition and antimicrobial coating material S7 according to the method identical with embodiment 1, different, while preparing antimicrobial coating composition, with 67 gram isopropyl alcohols, replace 67 gram ethanol.
Embodiment 8
The present embodiment is for illustrating complex antimicrobials provided by the invention, antimicrobial coating composition and antimicrobial coating material.
Prepare respectively complex antimicrobials A8, antimicrobial coating composition and antimicrobial coating material S8 according to the method identical with embodiment 1, different, while preparing antimicrobial coating composition, with 2 gram acetic acid, replace 2 gram citric acids.
Embodiment 9-12
The present embodiment is for illustrating the anti-microbial property of complex antimicrobials provided by the invention.
The anti-microbial property of antimicrobial coating material means with antibiotic rate.The antibiotic rate of the method that is QB/T 2591-2003 by the People's Republic of China's light industry standard standard No. complex antimicrobials A1-A4 that respectively prepared by test implementation example 1-4, wherein need respectively complex antimicrobials A1-A4 to be diluted with water to 10 % by weight, 0.2 weight, 0.03 % by weight, 10 % by weight, bacterial classification used is Escherichia coli (8099), staphylococcus aureus (ATCC6538).Test result when bacterial classification used is Escherichia coli (8099) is as shown in table 1 below, and test result when bacterial classification used is staphylococcus aureus (ATCC6538) is as shown in table 2 below.
Comparative Examples 4-6
This Comparative Examples is for illustrating the anti-microbial property of existing antibacterial agent.
Antibiotic rate with the antibacterial agent B1-B3 that respectively prepared by test comparison example 1-3 of the method described in embodiment 9-12, wherein need respectively antibacterial agent B1-B3 to be diluted with water to 0.03 % by weight, 0.03 weight, 0.03 % by weight, bacterial classification used is Escherichia coli (8099), staphylococcus aureus (ATCC6538).Test result when bacterial classification used is Escherichia coli (8099) is as shown in table 1 below, and test result when bacterial classification used is staphylococcus aureus (ATCC6538) is as shown in table 2 below.
Table 1
| Antibacterial agent | The concentration of antibacterial agent (% by weight) | Average clump count after 24 hours on 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 (% by weight) | Average clump count after 24 hours on 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, can find out, anticolibacillary antibiotic rate during 0.03 % by weight concentration of single antibacterial agent is 91.83-92.90%, will prepare RE (A) in CN 101120681A
c(B)
dNH
2Anticolibacillary antibiotic rate when the raw material of O mixes as 0.03 % by weight concentration of complex antimicrobials is 90.77%, and anticolibacillary antibiotic rate during 0.03 % by weight concentration of complex antimicrobials provided by the invention is 95.25%;
From the data of above-mentioned table 2, can find out, the antibiotic rate of anti-Staphylococcus aureus during 0.03 % by weight concentration of single antibacterial agent is 85.62-89.09%, will prepare RE (A) in CN 101120681A
c(B)
dNH
2The antibiotic rate of the anti-Staphylococcus aureus when raw material of O mixes as 0.03 % by weight concentration of complex antimicrobials is 85.00%, and the antibiotic rate of anti-Staphylococcus aureus during 0.03 % by weight concentration of complex antimicrobials provided by the invention is 93.92%;
Illustrated and will prepare RE (A) in CN 101120681A
c(B)
dNH
2The raw material of O, be about to rare earth ion, amino acid and azole heterocyclic compound and simply mix, and can not produce synergy, and complex antimicrobials provided by the invention can produce synergy.
Embodiment 13-20
The present embodiment is for illustrating the anti-microbial property of antimicrobial coating material provided by the invention.
Antibiotic rate with the antimicrobial coating material S1-S8 that respectively prepared by test implementation example 1-8 of the method described in embodiment 9-12, test result when bacterial classification used is Escherichia coli (8099) is as shown in table 3 below, and test result when bacterial classification used is staphylococcus aureus (ATCC6538) is as shown in table 4 below.
Comparative Examples 7-9
This Comparative Examples is for illustrating the anti-microbial property of existing antimicrobial coating material.
Antibiotic rate with the antimicrobial coating material C S1-CS3 that respectively prepared by test comparison example 1-3 of the method described in embodiment 9-12, test result when bacterial classification used is Escherichia coli (8099) is as shown in table 3 below, and test result when bacterial classification used is staphylococcus aureus (ATCC6538) is as shown in table 4 below.
Table 3
| The antimicrobial coating material | The concentration of antibacterial agent (% by weight) in composition | Average clump count after 24 hours on 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 (% by weight) in composition | Average clump count after 24 hours on 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, can find out, the anticolibacillary antibiotic rate while adopting the 0.03 % by weight concentration of the antimicrobial coating material C S1 of single antibacterial agent and CS2 is 82.68-85.31%, will prepare RE (A) in CN101120681A
c(B)
dNH
2Anticolibacillary antibiotic rate when the raw material of O mixes as the 0.03 % by weight concentration of the antimicrobial coating material C S3 of complex antimicrobials is 84.86%, and anticolibacillary antibiotic rate during the 0.03 % by weight concentration of antimicrobial coating material S1-S3 provided by the invention is 92.16%;
From the data of above-mentioned table 4, can find out, the antibiotic rate of the anti-Staphylococcus aureus while adopting the 0.03 % by weight concentration of the antimicrobial coating material C S1 of single antibacterial agent and CS2 is 81.33-84.00%, will prepare RE (A) in CN 101120681A
c(B)
dNH
2The antibiotic rate of the anti-Staphylococcus aureus when raw material of O mixes as the 0.03 % by weight concentration of the antimicrobial coating material C S3 of complex antimicrobials is 83.33%, and the antibiotic rate of anti-Staphylococcus aureus during the 0.03 % by weight concentration of antimicrobial coating material S1-S3 provided by the invention is 89.17%;
Illustrated and will prepare RE (A) in CN 101120681A
c(B)
dNH
2The raw material of O, be about to rare earth ion, amino acid and azole heterocyclic compound and simply mix, and can not produce synergy, and complex antimicrobials provided by the invention can produce synergy.
Claims (9)
1. a complex antimicrobials, this complex antimicrobials contains inorganic antiseptic and organic antibacterial agent, it is characterized in that, and the weight ratio of described inorganic antiseptic and organic antibacterial agent is 0.5-5:1; Described inorganic antiseptic is one or more in silver salt, silver oxide, mantoquita and copper oxide; The mixture that described organic antibacterial agent is isothiazolinone and BIT, wherein, in described mixture, the weight ratio of isothiazolinone and BIT is 1-5:1.
2. complex antimicrobials according to claim 1, wherein, described silver salt and mantoquita respectively do for oneself citrate and/or nitrate.
3. an 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 the alcohol that carbon number is 2-4, it is characterized in that, described antibacterial agent is the described complex antimicrobials of claim 1 or 2; Wherein, the gross weight of composition of take is benchmark, the content of described organosilicon and organic titanium is the 8-9 % by weight, the content of described organic complexing agent is the 2.5-3 % by weight, the content of described polar organic solvent is the 52.8-70 % by weight, and described inorganic acid and organic acid content are the 2-3 % by weight, and the content of described complex antimicrobials is the 0.03-10 % by weight, the content of described curing agent is the 0.3-2 % by weight, and the content of described thinner is the 10-30 % by weight.
4. antimicrobial coating composition according to claim 3, wherein, under non-working condition, curing agent independently exists.
5. antimicrobial coating composition according to claim 3, wherein, described organosilicon is one or more in ethyl orthosilicate, positive isopropyl silicate, vinyl silane triisopropoxide and vinyltrimethoxy silane, and described organic titanium is one or more in tetraethyl titanate, isopropyl titanate and tetrabutyl titanate; Described organic complexing agent is 2,4-pentanedione, 1, one or more in hydroresorcinol and ethyl acetoacetate; Described polar organic solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol and n-butanol; Described inorganic acid is one or more in hydrochloric acid, sulfuric acid and nitric acid, and described organic acid is one or more in acetic acid, citric acid and tartaric acid; Described curing agent is dibutyl tin laurate, ammonium acetate, 2, one or more in 4-diamino benzene sulfonic acid sodium and the mixture of 2,4-toluene di-isocyanate(TDI), and wherein, in this mixture 2, the content of 4-toluene di-isocyanate(TDI) is the 90-95 % by weight; Described thinner is 1-Methoxy-2-propyl acetate and/or butyl acetate.
6. antimicrobial coating composition according to claim 5, wherein, described organosilicon is vinyl silane triisopropoxide, described organic titanium is tetrabutyl titanate, described organic complexing agent is 2,4-pentanedione, and described polar organic solvent is ethanol, described inorganic acid is nitric acid, and described organic acid is citric acid.
7. an 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 the described antimicrobial coating composition of any one in claim 3-6.
8. antimicrobial coating material according to claim 7, wherein, the thickness of described antibiotic finishing coat is the 15-25 micron.
9. antimicrobial coating material according to claim 7, wherein, described base material is acrylonitrile/butadiene/styrene copolymer, polypropylene, Merlon and their complex, or stainless steel, titanium, magnesium, aluminium, zinc and their alloy.
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| WO2023284911A1 (en) * | 2021-07-12 | 2023-01-19 | Daxem GmbH | Coating composition |
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| 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 |
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| WO2023284911A1 (en) * | 2021-07-12 | 2023-01-19 | Daxem GmbH | Coating composition |
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