CN102702839B - In-tank antiseptic antimildew agent composition integrated with dry film for paint - Google Patents
In-tank antiseptic antimildew agent composition integrated with dry film for paint Download PDFInfo
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- CN102702839B CN102702839B CN201210222267.6A CN201210222267A CN102702839B CN 102702839 B CN102702839 B CN 102702839B CN 201210222267 A CN201210222267 A CN 201210222267A CN 102702839 B CN102702839 B CN 102702839B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Organic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The invention relates to an in-tank antiseptic antimildew agent composition integrated with a dry film for paint. The composition is prepared from a water-based paint in-tank antiseptic bactericide, a dry film antimildew agent, a solvent, an aid, a stabilizing agent and water. The in-tank antiseptic antimildew agent composition integrated with a dry film for paint has the advantages of reasonable formula, advanced process, good corrosion and mildew prevention effects, good stability, and the like. When the in-tank antiseptic antimildew agent composition integrated with a dry film for paint is used for paint, salt cluster phenomena can be avoided, an in-tank antiseptic effect can pass a microorganism challenge test, and the dry film mildew-growing grade is a zero grade.
Description
Technical field
The invention belongs to the preparing technical field of Chemical Preservation mould inhibitor, relate in a kind of tank of water-borne coatings and dry film Antisepticize and mildew preventive composition and method of making the same.
Background technology
Water-borne coatings produce and storage process in can suffer harmful microbe to pollute destruction, make coating color-changing, flatulence, smelly, breakdown of emulsion, precipitation, even lose practical value.Concerning many functional coatings or for the coating of special occasions, not only require coating to avoid microbial contamination at production storage process, and also should keep as far as possible the long life-span after paint brush is coated with film forming, to stop the erosion of bacterium, mould and algae.For example, for being applied to hospital, food-processing place, bathing place, villa district, (south China most area) house exterior wall, underground parking, the place that the high humidity such as tunnel, civil air defense constructions and installations, dark humidity, overcast and rainy phase are long, just wishes that coating films and have good fungus-proof antisepsis (algae) function.
After the in-can preservation agent of water-borne coatings and coating film forming, the mildew-resistant algaecide of (dry film) has larger difference in nature.In-can preservation agent is analyzed with regard to its active ingredient, mainly can be divided into isothiazolinone (as 5-chloro-2-methyl-4 isothiazoline-3-ketone, 2-methyl-4 isothiazoline-3-ketone, be called for short CMIT, MIT, general designation Kathon CG), release formaldehyde class is (as N-formal, O-formal, DMDMH, Sodium hydroxymethyl glycinate etc.), benzimidazoles is (as 1, 2-benzisothiazole-3-ketone, be called for short BIT), organic bromine class, organic amine, several classes such as piperazine triazines, it be take and suppresses in tank microbial reproduction growth and guarantee that in shelf-lives, coating never degenerates as object, the sanitas overwhelming majority used is water-soluble, easily dispersing and dissolving is in coating system, coating has generally just lost anti-corrosion function after using film forming.
The kind of current known dry film mould inhibitor is also a lot, by active ingredient, roughly have: isothiazolinone is (as 2-n-octyl-4 isothiazoline-3-ketone, abbreviation OIT), benzimidazoles, iodine propargyl class (2 propargyl butyl carbamates as iodo-in 3-are called for short IPBC), substituted arene class, dithiocarbamate(s) etc.In above-mentioned mould inhibitor, having many is that water and organic solvent are all undissolved, as Coating Antifungal Agents must be using it as emulsion or suspensoid preparation use.As everyone knows, disperse the mould inhibitor greatest drawback forming to be that its suspension stability is poor, again because of the restriction of the granule surface area of mould inhibitor own, it contacts difficulty with microorganism simultaneously, therefore bactericidal mould proof effect can not obtain maximum performance.
In prior art, coating is all with two kinds of additives, to add respectively when making coating with the dry film mould inhibitor after in-can preservation agent and use film forming, has so just caused the very big inconvenience of using.Dry film mould inhibitor provides commodity mainly with suspension greatly, efficiency is poor, be scattered in and in coating, need grinding distribution, in power consumption, owing to producing relatively high temperature, can affect the stability of sanitas, furthermore because coating material production business is limited to the understanding of this specialty goods of Antisepticize and mildew preventive, there will be the doubt of kind selection and dosage number, cause cost increasing or the anticorrosive mildewproof effect of product not good.For general Antisepticize and mildew preventive manufacturer, how in-can preservation agent and dry film mildew-resistant are organically combined and still had very large technical difficulty, main because there is no effective stabilization technique, particularly this efficient in-can preservation agent of CMIT, MIT and other dry film mould inhibitor can be combined suitably and do not brought into the technology of divalent-metal ion.Because if do not need special stable sanitas and dry film mould inhibitor to combine (as: by MIT and the combination of dry film mould inhibitor some, or by BIT and the combination of dry film mould inhibitor), the anticorrosive mildewproof effect of product will be difficult to realize very poor and economically, meanwhile, the antimicrobial spectrum of composition complementarity, consistency etc. also all also need a large amount of Experiment on Microbiology screenings.Due to above reason, up to now, on market, still also do not have in-can preservation agent and dry film anti-fungus agent composition to occur.
Summary of the invention
The problem that the object of the invention is to prior art to exist is solved, and provides a kind of coating reasonable, technique is advanced, anticorrosive mildewproof is effective of filling a prescription to use in tank and the integrated Antisepticize and mildew preventive composition and method of making the same of dry film.
For realizing foregoing invention object and the coating that provides with in tank and the effective constituent of the integrated Antisepticize and mildew preventive composition of dry film by the raw material of substance of following weight per-cent, formed:
Biocides Used for In-Can Waterborne Coatings Preservation 2%～10%,
Dry film mould inhibitor 15%～35%,
Solvent 40%～60%,
Auxiliary agent 0.1%～5%,
Stablizer 1%～10%,
Surplus is water;
Wherein, said Biocides Used for In-Can Waterborne Coatings Preservation is one or more in following substances: 2-methylisothiazolinone, the Kathon CG (mixture of 2-methylisothiazolinone and 5-chloro-2-methyl isothiazolinone, be CMIT/MIT), 1,2 BITs, bronopol (Bronopol), Phenoxyethanol, formaldehyde sustained release dosage (N-formal, O-formal), 1,3,5-tri-(2-hydroxyethyl)-s-triazine, wherein, when two kinds of in-can preservation sterilant compound uses, another kind of in-can preservation sterilant is called synergy sanitas; Said dry film mould inhibitor is one or more in following substances: DCOIT (4,5 two chloro-2-n-octyl-4 isothiazoline-3-ketone), OIT (2-n-octyl-4 isothiazoline-3-ketone), IPBC (iodo-2 propargyl butyl carbamates of 3-), ZPT (Zinc Pyrithione), BCM (benzoglyoxaline Urethylane, another name derosal), oxine, TPN (m-tetrachlorophthalodinitrile), TBZ (Top Form Wormer, thiabendazole); Said solvent is one or more in following substances: 1,2 propylene glycol, polyoxyethylene glycol, dipropylene glycol, propylene glycol phenylate, ethylene glycol; Said auxiliary agent is solubilizing agent, adopts hydrogenated castor oil or TX-10 (alkylphenol polyoxyethylene); Said stablizer is SODIUMNITRATE, lithium nitrate, saltpetre, benzoyl peroxide.
Make coating of the present invention with in tank with preferred weight part ratio range of the raw material of substance of the integrated Antisepticize and mildew preventive composition of dry film being:
Biocides Used for In-Can Waterborne Coatings Preservation 2%～8%,
Dry film mould inhibitor 25%～35%,
Solvent 40%～50%,
Auxiliary agent 0.2%～3%,
Stablizer 1%～6%,
Surplus is water.
Technical solution of the present invention is also: said Biocides Used for In-Can Waterborne Coatings Preservation is one or more in following substances: 2-methylisothiazolinone, Kathon CG, 1,2 BIT, bronopol; Said dry film mould inhibitor is one or more in following substances: DCOIT, OIT, IPBC, ZPT; Said solvent is one or more in following substances: 1,2 propylene glycol, polyoxyethylene glycol, ethylene glycol; Said auxiliary agent is TX-10; Said stablizer is SODIUMNITRATE and benzoyl peroxide.
Technical solution of the present invention is also: said Biocides Used for In-Can Waterborne Coatings Preservation is Kathon CG; Said dry film mould inhibitor is OIT and IPBC; Said solvent is 1,2 propylene glycol.
For the preparation of this coating with comprising following processing step with the method for the integrated Antisepticize and mildew preventive composition of dry film in tank:
1, the Biocides Used for In-Can Waterborne Coatings Preservation obtaining after thiopropionamide cyclisation is dissolved in deionized water, with alkali, neutralize pH and be about 2～4, adjusting Biocides Used for In-Can Waterborne Coatings Preservation content is 10%～15%, add 85%～100% stablizer of stablizer total amount to stir, filter stand-by;
2 add synergy sanitas stirring and dissolving in the solution obtaining after above-mentioned steps 1 again;
3, the dry film mould inhibitor of dry film mould inhibitor total amount 5%～10% is first dissolved in solvent, and then adds the dry film mould inhibitor of rest part to stir, then add the stablizer of auxiliary agent and surplus to stir evenly;
4, under agitation condition, add the in-can preservation agent obtaining after above-mentioned steps 2;
5, be uniformly mixed, filter.
Preparation method's of the present invention technical solution is also: the said Biocides Used for In-Can Waterborne Coatings Preservation of above-mentioned steps 1 for after thiopropionamide cyclisation, obtain not containing the Kathon CG sanitas of divalence magnesium, calcium, cupric ion, the weight blending ratio of CMIT in Kathon CG sanitas (5-chloro-2-methyl-4 isothiazoline-3-ketone) and MIT (2-methyl-4 isothiazoline-3-ketone) is 2～4: 1.
Preparation method's of the present invention technical solution is also: the said solvent of above-mentioned steps 3 is 1,2 propylene glycol, and said dry film mould inhibitor is OIT and IPBC, mould inhibitor IPBC is first dissolved in to 1, in 2 propylene glycol, then add OIT to stir, then add solubilizing agent to stir evenly.
The invention has the beneficial effects as follows:
One, the present invention adopts the stable preparation method of uses advanced, makes in-can preservation agent be brought into play classic effect, and composite other synergy sanitas makes it have superpower antisepsis and sterilization ability simultaneously; Due to not containing divalence magnesium, calcium, cupric ion, can effectively avoid " salt bunch " effect of film forming macromolecule emulsion in coating, and realize and having complementary advantages according to the antimicrobial spectrum of relevant sanitas, science compatibility forms compound preservative.The existing in-can preservation agent in the relative market of this compound preservative has distinct characteristic and comprises: (1). take into account quick sterilization and long-time Antifungal activity, (2). the antimicrobial spectrum of several sanitass can be complementary, (3). the protection domain of sanitas (space) strengthens, (4). the potential of hydrogen of sanitas (pH value) scope of application expands, (5). sanitas consumption reduces, toxicity reduces, security improves, (6). high low-temperature stability improves, (7). compound preservative use cost reduces, (8). the compound better adaptability of sanitas of different sterilization mechanisms, (9). effectively prevent the resistance of microorganism to sanitas,
Two, use anticorrosion with coat mould inhibitor of the present invention can reduce the production cost of coating, reduce the add-on 20%～50% of thickening material in coating, improve the rheological characteristics of coating, can effectively resist harmful microbe resistance in coating;
Three, the present invention scientifically combines in-can preservation and dry film mould inhibitor, to coating production enterprise, use and bring great convenience, and reduce and repeat transportation, the expense that repeated packing is brought and environmental protection pressure, and therefore cause cost to strengthen or the not good defect of anticorrosive mildewproof effect;
Four, the compatibleness of protective system of the present invention and coating is good;
Five, the present invention's anticorrosive mildewproof component used toxicity is low, all, in the listed scope of industrial sanitas, is at home and abroad used widely;
Six, coating of the present invention, with simple to operate with the production method of the integrated Antisepticize and mildew preventive composition of dry film in tank, is easy to realize scale production.
Coating of the present invention is used in tank and the good stability of the integrated Antisepticize and mildew preventive of dry film, product normal temperature storage is carried out application test after half a year, through departments such as Shaanxi Institute of Microbiology, detect, exterior wall mildew level estimate reaches the related products (table 1) of external famous sanitas company, in-can preservation performance has been passed through mixing microorganisms challenge test (table 2), result of use is desirable, has reached object of the present invention.
In mildew-resistant level estimate, postvaccinal sample is placed under the temperature and humidity of regulation and cultivates, regularly ventilation, finally with magnifying glass from the situation of growing positive and side observation spore, mycelia and bacterium colony, provide the judgement of mildew grade; Mixing microorganisms is added in exterior coating, then add coating of the present invention with in tank with the integrated Antisepticize and mildew preventive composition of dry film, regularly detect the wherein growth and breeding situation of bacterium and mould, after 28 days, provide challenge result.The bacterial classification adding is mixed bacterium, Pseudomonas aeruginosa, streptococcus aureus, intestinal bacteria, Candida albicans bacterium, black-koji mould, penicillium funiculosum, viride.Test concentrations: sanitas is add-on 0.2% in exterior coating.
Table 1 mildew level estimate result
The mixing microorganisms challenge test of table 2 in-can preservation
Embodiment
Embodiment 1
Take 20 kilograms of CMIT/MIT hydrochlorides, be dissolved in 70 kilograms of deionized waters, with alkaline agent sodium bicarbonate, neutralizing pH is 2～4, adds 3 kilograms of SODIUMNITRATE, filters, and mends total amount be double centner with deionized water, standby.
Get 16 kilograms of said mixtures, stir and add 4 kilograms of bronopol synergy sanitass, obtain coating antiseptic in composite tanks.
Get 47 kilograms of 1,2 propylene glycol, add IPBC3 kilogram of dissolving; Add again OIT30 kilogram of dissolving, finally add 0.2 kilogram of 0.2 kilogram of non-ionic surfactant TX-10 (auxiliary agent) and benzoyl peroxide (stablizer) and stir, if desired heating for dissolving; Under stirring, add 19.6 kilograms of the interior sanitass of composite tanks, disperse to stir 30 minutes; With 100 order stainless (steel) wires, filter, obtain invention product.
Embodiment 2
Take 20 kilograms of CMIT/MIT hydrochlorides, be dissolved in 70 kilograms of deionized waters, with alkaline agent sodium bicarbonate, neutralizing pH is 2～4, adds 5 kilograms of dissolvings of saltpetre, filters, and mends total amount be double centner with deionized water, standby.
Get 20 kilograms of said mixtures, obtain coating antiseptic in tank.
Get 47 kilograms of 1,2 propylene glycol, add IPBC3 kilogram of dissolving; Add again OIT30 kilogram of dissolving, if desired heating for dissolving; Under stirring, add 0.3 kilogram of 20 kilograms of coating antiseptics in tank, 0.2 kilogram of TX-10 (auxiliary agent) and benzoyl peroxide, disperse to stir 30 minutes.With 100 order stainless (steel) wires, filter, obtain invention product.
Embodiment 3
Take 16 kilograms of 50%MIT sanitass, then add 4 kilograms of dissolvings of bronopol, controlling pH is 2～4, gets said mixture and obtains coating antiseptic in composite tanks.
Get 47 kilograms of 1,2 propylene glycol, add IPBC3 kilogram of dissolving; Add again OIT30 kilogram of dissolving, then add 0.3 kilogram of TX-10 (auxiliary agent), if desired heating for dissolving; Under stirring, add 19.7 kilograms of the interior sanitass of composite tanks, disperse to stir 30 minutes, with 100 order stainless (steel) wires, filter, obtain invention product.
Embodiment 4
Take 20 kilograms of CMIT/MIT hydrochlorides, be dissolved in 70 kilograms of deionized waters, with alkaline agent, neutralizing pH is 2-4, adds 4 kilograms of SODIUMNITRATE, filters, and with deionized water, mending total amount is double centner, standby.
Get 15 kilograms of said mixtures, obtain coating antiseptic in tank.
Get 50 kilograms of 1,2 propylene glycol, add IPBC3 kilogram, BIT3 kilogram dissolving; Add OIT30 kilogram, 0.2 kilogram of TX-10 (auxiliary agent) and 0.3 kilogram of stirring and dissolving of benzoyl peroxide, if desired can heating for dissolving again; Under stirring, add 20 kilograms of in-can preservation agent, disperse to stir 30 minutes, with 100 order stainless (steel) wires, filter, obtain invention product.
Claims (8)
- Coating with in tank with the integrated Antisepticize and mildew preventive composition of dry film, the effective constituent that it is characterized in that said composition is prepared from by the raw material of substance of following weight per-cent:Biocides Used for In-Can Waterborne Coatings Preservation 2%～10%,Dry film mould inhibitor 15%～35%,Solvent 40%～60%,Auxiliary agent 0.1%～5%,Stablizer 1%～10%,Surplus is water;Said Biocides Used for In-Can Waterborne Coatings Preservation is one or more in following substances: 2-methylisothiazolinone, Kathon CG, 1,2 BITs, bronopol, Phenoxyethanol, formaldehyde sustained release dosage, 1,3,5-tri-(2-hydroxyethyl)-s-triazine, wherein, when two kinds of in-can preservation sterilant compound uses, another kind of in-can preservation sterilant is synergy sanitas; Said dry film mould inhibitor is one or more in following substances: DCOIT, OIT, IPBC, ZPT, BCM, oxine, TPN, TBZ; Said solvent is one or more in following substances: 1,2 propylene glycol, polyoxyethylene glycol, dipropylene glycol, propylene glycol phenylate, ethylene glycol; Said auxiliary agent is hydrogenated castor oil or TX-10; Said stablizer is one or more in following substances: SODIUMNITRATE, lithium nitrate, saltpetre, benzoyl peroxide.
- Coating according to claim 1 with in tank with the integrated Antisepticize and mildew preventive composition of dry film, the effective constituent that it is characterized in that said composition is prepared from by the raw material of substance of following weight per-cent:Biocides Used for In-Can Waterborne Coatings Preservation 2%～8%,Dry film mould inhibitor 25%～35%,Solvent 40%～50%,Auxiliary agent 0.2%～3%,Stablizer 1%～6%,Surplus is water.
- 3. coating according to claim 1 is used in tank and the integrated Antisepticize and mildew preventive composition of dry film, it is characterized in that said Biocides Used for In-Can Waterborne Coatings Preservation is one or more in following substances: 2-methylisothiazolinone, Kathon CG, 1,2 BIT, bronopol; Said dry film mould inhibitor is one or more in following substances: DCOIT, OIT, IPBC, ZPT; Said solvent is one or more in following substances: 1,2 propylene glycol, polyoxyethylene glycol, ethylene glycol; Said auxiliary agent is TX-10; Said stablizer is SODIUMNITRATE and benzoyl peroxide.
- According to coating described in claim 1 or 3 with in tank with the integrated Antisepticize and mildew preventive composition of dry film, it is characterized in that said Biocides Used for In-Can Waterborne Coatings Preservation is Kathon CG; Said dry film mould inhibitor is OIT and IPBC; Said solvent is 1,2 propylene glycol.
- For the preparation of coating described in claim 1 with in tank with the method for the integrated Antisepticize and mildew preventive composition of dry film, it is characterized in that comprising following processing step:5.1 are dissolved into the Biocides Used for In-Can Waterborne Coatings Preservation obtaining after thiopropionamide cyclisation in deionized water, with alkali, neutralize pH rapidly and be about 2～4, adjusting Biocides Used for In-Can Waterborne Coatings Preservation content is 10%～15%, add the stablizer of stablizer total amount 85%～100% to stir, filter stand-by;5.2 add synergy sanitas stirring and dissolving in the solution obtaining after step 5.1 again;5.3 are first dissolved in the dry film mould inhibitor of dry film mould inhibitor total amount 5%～10% in solvent, and then add the dry film mould inhibitor of rest part to stir, then add the stablizer of auxiliary agent and surplus to stir evenly;5.4 add the in-can preservation agent obtaining after step 5.2 under agitation condition;5.5 are uniformly mixed, and filter.
- 6. preparation method according to claim 5, is characterized in that the Kathon CG sanitas of the said Biocides Used for In-Can Waterborne Coatings Preservation of step 5.1 for obtaining after thiopropionamide cyclisation.
- 7. preparation method according to claim 6, is characterized in that in Kathon CG sanitas, the weight blending ratio of CMIT and MIT is 2～4: 1.
- 8. preparation method according to claim 5, is characterized in that the said solvent of step 5.3 is 1,2 propylene glycol, said dry film mould inhibitor is OIT and IPBC, and mould inhibitor IPBC is first dissolved in 1,2 propylene glycol, then add OIT to stir, then add solubilizing agent to stir evenly.
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| CN201210222267.6A CN102702839B (en) | 2012-06-29 | 2012-06-29 | In-tank antiseptic antimildew agent composition integrated with dry film for paint |
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| CN201210222267.6A CN102702839B (en) | 2012-06-29 | 2012-06-29 | In-tank antiseptic antimildew agent composition integrated with dry film for paint |
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| WO2018044641A1 (en) * | 2016-08-30 | 2018-03-08 | Rohm And Haas Company | Synergistic combination of lenacil and 1,2-benzisothiazol-3(2h)-one |
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| CN113321977A (en) * | 2021-06-17 | 2021-08-31 | 中节能(唐山)环保装备有限公司 | Water-based antibacterial and mildewproof coating and preparation method thereof |
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