CN100357376C - Mould proof antibacterial ultraviolet film and its preparing method - Google Patents

Mould proof antibacterial ultraviolet film and its preparing method Download PDF

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Publication number
CN100357376C
CN100357376C CNB2005100479318A CN200510047931A CN100357376C CN 100357376 C CN100357376 C CN 100357376C CN B2005100479318 A CNB2005100479318 A CN B2005100479318A CN 200510047931 A CN200510047931 A CN 200510047931A CN 100357376 C CN100357376 C CN 100357376C
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ultraviolet film
antibacterial ultraviolet
preparation
mould proof
vinylformic acid
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CNB2005100479318A
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CN1775878A (en
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徐忠斌
杨淑琴
娄虹
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Liaoning University
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Liaoning University
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Abstract

The present invention provides a mildewproof antibacterial ultraviolet film and a preparation method thereof, which relates to antibacterial paint and a preparation method thereof, particularly to a mildewproof antibacterial ultraviolet film suitable for paper, metal and plastics and a preparation method thereof. The mildewproof antibacterial ultraviolet film comprises the raw materials of epichlorohydrin, acrylic acid, epoxy resin, p-hydroxyanisole, tetrabutylammonium bromide, triethanolmine, benzophenone, 3-propylene glycol-2-acrylate ester, 3-hydroxymethyl-3-acrylate ester, 2, 2-dimethoxy-1, 2-diphenylethanone, a silver and zinc ion germicide, a dispersion agent, etc. which are prepared by proper steps according to a certain proportion. The present invention has the advantages of broad-spectrum antibacterial function, high bacteriostasis ratio, long continuous effective time, no poison and no harm; when the mildewproof antibacterial ultraviolet film is applied to the receptors of the paper, the metal, the plastics, etc., the brightness of the mildewproof antibacterial ultraviolet film can prevent moisture and mildew; the present invention is useful for public sanitation and the avoidance of large-area explosion of infectious diseases.

Description

Mould proof antibacterial ultraviolet film and preparation method thereof
Technical field:
The present invention relates to antibiotic paint and preparation method thereof, especially a kind of mould proof antibacterial ultraviolet film that is applicable to paper, metal, plastics and preparation method thereof.
Background technology:
Be to solve the diseases prevention of high-density population, immunization issues, reduce the probability that big area breaks out pernicious communicate illness, we wish that like this, using antiseptic-germicide on articles for use is good method the daily articles for use that contact of people disease carrying germ not as far as possible.
At present, general organic drug (antiseptic-germicide that has) has great limitation on thermotolerance, weathering resistance, the anti-time property in security, be difficult for degraded, and pollution is arranged, and is unsuitable for the antiseptic-germicide as articles for daily use; So just inorganic antiseptic is studied, inorganic antiseptic is the 1980s, at first grow up from Japan, be countries such as France, Italy, the U.S. afterwards, China is from the development that begins one's study of eighties of last century the nineties, preliminary achievement has been arranged, but also had certain distance apart from practical application.
We have obtained silver-colored zine ion has very good effect as inorganic antiseptic conclusion, but, lose antibiotic effectiveness owing to silver ions is easy to change, this just makes this kind antiseptic-germicide be difficult to make its performance antibacterial efficacy for a long time on the real various articles for use that are administered in the daily life.
In daily life, we often touch a lot of paper, metal, plastics, they do not have anti-microbial effect usually, especially school, the market, bus, intensive and the mobile very large place of personnel such as station, germ is attached to books, commodity, on vehicle seat and the various vessel, they have the potential threat to people's health, in the big area disease transmission, will danger close and loses function in these places, over and done with SARS has told the fearful of this situation, can make a kind of coating that contains top inorganic antiseptic and cover paper, metal, on the vessel such as plastics, this coating can continuous and effective antibacterial, and make the local bacterium of the daily contact of people, virus, can not microorganisms such as mould survive, thereby make people obtain higher safety assurance?
Summary of the invention:
Silver ion antimicrobial agent is easy to change to lose germicidal action in order to solve, and the problem that can not use on a large scale the invention provides a kind of slowly delivery of antimicrobials, can be in long-time mould proof antibacterial ultraviolet film and preparation method thereof of an anti-microbial effect.
Mould proof antibacterial ultraviolet film comprises that following raw material makes by following weight part:
Epoxy acrylic resin 30~50
Thinner 30~90
Trolamine 0.2~2
Benzophenone 0.2~5
2,2-dimethoxy-1,2-phenylbenzene ethyl ketone or
Benzoin dimethylether or both mixtures 0.5~4
Silver zine ion sterilant 0.5~4.
For making silver-colored zine ion sterilant dispersed uniform in finished product, add dispersion agent, select aerosil 0.1~2 weight part.
For avoiding the filmogen spontaneous polymerization under light-initiated condition not in the coating, add stopper, should contain MEHQ 0.4~0.6 weight part in the finished product.
Thinner is the mixture of epoxy chloropropane-vinylformic acid or tripropylene glycol diacrylate or tri methylol triacrylate or epoxy chloropropane-vinylformic acid and tripropylene glycol diacrylate or mixture or the mixture of tripropylene glycol diacrylate and tri methylol triacrylate or the mixture of epoxy chloropropane-vinylformic acid and tripropylene glycol diacrylate and tri methylol triacrylate of epoxy chloropropane-vinylformic acid and tri methylol triacrylate.
This thinner of epoxy chloropropane-vinylformic acid comprises that following raw material makes according to following weight part:
Epoxy chloropropane 200~300
Vinylformic acid 150~200
MEHQ 0.08~0.1
Tetrabutyl amonium bromide or trolamine 3~6
Epoxy acrylic resin comprises that following raw material makes according to following weight part:
Resins, epoxy 180~240
Vinylformic acid 50~100
MEHQ 0.2~0.6
Tetrabutyl amonium bromide or trolamine 1~3
The preparation method of mould proof antibacterial ultraviolet film, press above-mentioned weight ratio with thinner and epoxy acrylic resin, benzophenone, 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone, trolamine mixes, and adds silver-colored zine ion sterilant again, the aerosil that adds above-mentioned amount again stirs and makes finished product.
Make finished product and be applied on the acceptor, the UV-irradiation film forming.
The preparation method of this thinner of epoxy chloropropane-vinylformic acid is:
With in 200~300Kg epoxy chloropropane suction reactor and start stirring, under agitation 0.08~0.10Kg MEHQ is added in the reactor;
With 150~200Kg vinylformic acid and the dissolving of 3~6Kg Tetrabutyl amonium bromide; Perhaps the trolamine with 150~200Kg vinylformic acid and 3~6Kg mixes;
Epoxy chloropropane and MEHQ slowly are warming up to 108~115 ℃;
When epoxy chloropropane and MEHQ temperature rise to 108~115 ℃, vinylformic acid that dissolving is good and Tetrabutyl amonium bromide or vinylformic acid and trolamine uniform acceleration begin to drip; Dropping temperature 110-125 ℃, 2.5~3 hours dropping time, 120-125 ℃ of reaction 2 hours, react back sampling analysis acid number after adding, acid number 1~5 is qualified, if defective continuation is incubated 120-125 ℃ until qualified.
The preparation method of epoxy acrylic resin is:
180~240Kg Resins, epoxy and 0.20~0.60Kg MEHQ are added in the reactor;
With 50~100Kg vinylformic acid and the dissolving of 1~3Kg Tetrabutyl amonium bromide; Perhaps the trolamine with 50~100Kg vinylformic acid and 1~3Kg mixes;
Lentamente Resins, epoxy and MEHQ are warming up to 58~63 ℃, stir, temperature rises to 98~110 ℃ and begins to drip dissolving good vinylformic acid and Tetrabutyl amonium bromide or vinylformic acid and trolamine, dropping temperature 110-125 ℃, 3~3.5 hours dropping time; Add the back control reaction temperature 120-125 ℃ of reaction 1 hour, reaction back sampling analysis acid number, acid number 1~5 be qualified, if defective continuation is incubated 120-125 ℃ till qualified, is cooled to 85~95 ℃ of blowings after qualified.
Above-mentioned raw materials is technical pure;
Silver zine ion sterilant is that argentiferous zine ion ratio is 1~3: 5~6 on the carriers such as hydroxyapatite, porous zeolite, can be buied by gloomy logical great group in Beijing;
Resins, epoxy is E51 model 628,826.
Beneficial effect of the present invention: the finished product of the present invention preparation not with an organic solvent, itself does not have toxicity, the light film characteristics of its formation have the function of light, wrinkle resistant, moistureproof, mildew-resistant again, to particularly suitable in the easily damp easily mould article of easy wrinkles easy to break such as paper; Coating can slowly discharge silver ions, and silver ions has very strong broad-spectrum antibacterial action, and harmless, easily degraded, and environmental sound, validity period can reach more than 8 years.
Be applied in the process that their are propagated, avoid the propagation of microorganism among the media such as paper anti-the infection, students in middle and primary schools' textbook can recycle like this, reduce the resource of country and student's burden, build a conservation-minded society, huge economic benefit and social benefit are arranged.
It also is the same that the present invention is applied on other the object metal, plastics, continues efficiently antibacterial.
Bacteriostatic experiment
This light film through Institute for Environment Hygiene and Health Related Product Safety, China CDC according to " disinfection technology standard " (version in 2002) 2.1.8.9 item carry out Quinn test (sample is accepted numbering: 2003K876), test-results is:
1, through three revision tests, the result shows: during control group growth bacterium number>100cfu/ sheet, mould proof antibacterial ultraviolet film is 99.99% to the average bacteriostasis rate of streptococcus aureus, shows that mould proof antibacterial ultraviolet film has bacteriostatic action to streptococcus aureus.
2, through three revision tests, the result shows: during control group growth bacterium number>100cfu/ sheet, mould proof antibacterial ultraviolet film is 99.96% to colibacillary average bacteriostasis rate, shows that mould proof antibacterial ultraviolet film has bacteriostatic action to intestinal bacteria.
Embodiment
Embodiment 1: mould proof antibacterial ultraviolet film, make by following weight part by following raw material:
Epoxy acrylic resin 30~50
Thinner 30~90
Trolamine 0.2~2
Benzophenone 0.2~5
2,2-dimethoxy-1,2-phenylbenzene ethyl ketone or
Benzoin dimethylether or both mixtures 0.5~4
Silver zine ion sterilant 0.5~4
Aerosil 0.1~2.
Embodiment 2: epoxy chloropropane-acrylic diluents, make according to following weight part by following raw material:
Epoxy chloropropane 200~300
Vinylformic acid 150~200
MEHQ 0.08~0.1
Tetrabutyl amonium bromide or trolamine 3~6.
Embodiment 3: epoxy acrylic resin, make by the following weight part of following raw material:
Resins, epoxy 180~240
Vinylformic acid 50~100
MEHQ 0.2~0.6
Tetrabutyl amonium bromide or trolamine 1~3.
Embodiment 4: the preparation of this thinner of epoxy chloropropane-vinylformic acid:
The bottom valve of 1000 liters of reactors cuts out and conscientiously check, the back, under agitation adds the 0.096Kg MEHQ in the reactor in 1000 liters of reactors of 240Kg epoxy chloropropane suction and start stirring with vacuum pump then;
In 186.7Kg vinylformic acid and 4.8Kg Tetrabutyl amonium bromide or the good also suction scale tank of dissolving, wait after being ready to drip and use;
Open the condenser water supply valve door above the reactor and open steam valve and lentamente epoxy chloropropane and MEHQ are warming up to 110 ℃; Temperature is effective in 108~115 ℃ of scopes.
When temperature rises to 110 ℃,, begin dropping with stable speed with good acrylic acid and the Tetrabutyl amonium bromide of dissolving in the scale tank; Dropping temperature 110-125 ℃, 2.5~3 hours dropping time; Maintain the temperature at 120-125 ℃ of internal reaction 2 hours after adding, sampling analysis acid number after the insulation reaction, acid number 1~5 is qualified.If 120-125 ℃ of defective continuation insulation is till qualified.After this close stirring, condenser upper hose valve, cooling is stand-by naturally.
Embodiment 5: the preparation of this thinner of epoxy chloropropane-vinylformic acid: reaction conditions and step are constant as embodiment 4, change the input weight such as the following table of various raw materials: (unit: Kg)
1 2 3 4 5 6 7 8 9
Epoxy chloropropane 200 210 220 225 230 250 260 280 300
Vinylformic acid 150 160 170 175 180 190 190 200 200
MEHQ 0.08 0.085 0.087 0.09 0.092 0.096 0.097 0.1 1
Tetrabutyl amonium bromide 3 3.5 4 4.3 4.7 5 5.5 6 6
Embodiment 6: the preparation of this thinner of epoxy chloropropane-vinylformic acid: reaction conditions and step are constant as embodiment 4, and the input weight of various raw materials such as embodiment 5 tables replace Tetrabutyl amonium bromide with weight such as trolamines.
Embodiment 7: the preparation of epoxy acrylic resin:
The bottom valve of 1000 liters of reactions cuts out and conscientiously check, after closing 200Kg Resins, epoxy and 0.4Kg MEHQ are added in the reactor;
In 75Kg vinylformic acid dissolving 2Kg Tetrabutyl amonium bromide and suction scale tank, wait after being ready to drip and use;
Open the condenser water supply valve door above the reactor and open steam valve and Resins, epoxy is warming up to 59~63 ℃ lentamente and starts stirring; When rising to 100~110 ℃, temperature begins to drip good vinylformic acid and the Tetrabutyl amonium bromide of dissolving in the scale tank; Controlled temperature 110-125 ℃, the period was at 3~3.5 hours; Maintain the temperature at 120-125 ℃ of reaction 1 hour after adding, sampling analysis acid number after the insulation reaction, acid number 1~5 is qualified; If 120-125 ℃ of defective continuation insulation is till qualified; Be cooled to 90 ℃ of blowings after qualified; It is medium to be used to emit material input priming paint, closes stirring, water coolant, condenser upper hose valve simultaneously.
Embodiment 8: the preparation of epoxy acrylic resin: reaction conditions and step are with embodiment 7, and each raw material is thrown in weight such as following table: (unit: Kg)
1 2 3 4 5 6 7 8 9
Resins, epoxy 180 185 190 195 205 210 215 220 240
Vinylformic acid 50 60 65 65 73 75 80 90 100
MEHQ 0.2 0.3 0.35 0.38 0.42 0.45 0.48 0.5 0.6
Tetrabutyl amonium bromide 1 1.4 1.6 1.8 2.1 2.3 2.5 2.8 3
Embodiment 9: the preparation of epoxy acrylic resin: reaction conditions and step are with embodiment 7, and each raw material is thrown in weight such as embodiment 8, replace Tetrabutyl amonium bromide with weight such as trolamines.
Embodiment 10: the preparation mould proof antibacterial ultraviolet film:
Get the epoxy chloropropane-acrylic diluents 40Kg of above-mentioned preparation, epoxy acrylic resin 40Kg mixes, add the 2Kg benzophenone and add 2Kg2,2-dimethoxy-1,2-phenylbenzene ethyl ketone adds the 1Kg trolamine again, adding 10Kg tripropylene glycol diacrylate and 10Kg tri methylol triacrylate mixes, add 2Kg silver zine ion sterilant again, add the 1Kg aerosil again, mixing and stirring is finished product.UV-irradiation film forming when being applied to object.
Embodiment 11: the preparation mould proof antibacterial ultraviolet film: raw material stage such as embodiment 10, change feed intake weight such as following table (unit: Kg):
1 2 3 4 5 6 7 8 9
Ring-acrylic diluents 30 ?32 ?33 ?35 ?38 ?43 ?45 ?50 ?60
Epoxy acrylic resin 30 ?33 ?36 ?38 ?41 ?42 ?43 ?45 ?50
Benzophenone 0.2 ?1 ?1.4 ?1.8 ?2 ?2.3 ?3 ?4 ?5
2,2-dimethoxy-1,2-phenylbenzene ethyl ketone 0.5 ?1 ?1.5 ?1.8 ?2 ?2.2 ?2.5 ?3 ?4
Trolamine 0.2 ?0.5 ?0.6 ?0.8 ?1 ?1.2 ?1.4 ?1.6 ?2
Tripropylene glycol diacrylate 0 ?6 ?7 ?8 ?9 ?11 ?12 ?14 ?15
Tri methylol triacrylate 0 ?6 ?7 ?8 ?9 ?11 ?12 ?14 ?15
Silver zine ion sterilant 0.5 ?1 ?1.5 ?1.8 ?2 ?2.2 ?2.5 ?3 ?4
Aerosil 0.1 ?0.5 ?0.7 ?0.9 ?1 ?1.2 ?1.4 ?1.6 ?2
Annotate: ring-acrylic diluents is epoxy chloropropane-acrylic diluents.
Embodiment 12: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, each raw material is thrown in weight such as embodiment 11, replaces tripropylene glycol diacrylate and tri methylol triacrylate with weight such as this thinners of homemade epoxy chloropropane-vinylformic acid.
Embodiment 13: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, each raw material is thrown in weight such as embodiment 11, replaces self-control this thinner of epoxy chloropropane-vinylformic acid and tri methylol triacrylate with weight such as tripropylene glycol diacrylates.
Embodiment 14: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, each raw material is thrown in weight such as embodiment 11, replaces self-control this thinner of epoxy chloropropane-vinylformic acid and tripropylene glycol diacrylate with weight such as tri methylol triacrylates.
Embodiment 15: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, and each raw material is thrown in weight such as embodiment 11, replace tri methylol triacrylate with weight such as tripropylene glycol diacrylates.
Embodiment 16: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, and each raw material is thrown in weight such as embodiment 11, replace tripropylene glycol diacrylate with weight such as tri methylol triacrylates.
Embodiment 17: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, and each raw material is thrown in weight such as embodiment 11, replace this thinner of self-control epoxy chloropropane-vinylformic acid with weight such as tri methylol triacrylates.
Embodiment 18: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, and each raw material is thrown in weight such as embodiment 11, replace this thinner of self-control epoxy chloropropane-vinylformic acid with weight such as tripropylene glycol diacrylates.
Embodiment 19: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, and each raw material type and input weight such as embodiment 11~18 replace 2 with weight such as benzoin dimethylethers, 2-dimethoxy-1,2-phenylbenzene ethyl ketone.
Embodiment 20: the preparation mould proof antibacterial ultraviolet film: reaction conditions and step are with embodiment 10, each raw material type and input weight such as embodiment 11~18, with benzoin dimethylether and 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone mixes weight replacements 2 such as back with arbitrary proportion, 2-dimethoxy-1,2-phenylbenzene ethyl ketone.
The specific embodiment of the invention is not limited to above several.
Above-mentioned raw materials is a technical pure;
Silver zine ion sterilant is that argentiferous zine ion ratio is 1~3: 5~6 on the carriers such as hydroxyapatite, porous zeolite; Can buy by gloomy logical great group in Beijing;
Resins, epoxy is E51 model 628,826.

Claims (5)

1, mould proof antibacterial ultraviolet film is characterized in that comprising that following raw material makes by following weight part:
Epoxy acrylic resin 30~50
Thinner 30~90
Trolamine 0.2~2
Benzophenone 0.2~5
2,2-dimethoxy-1,2-phenylbenzene ethyl ketone or
Benzoin dimethylether or both mixtures 0.5~4
Silver zine ion sterilant 0.5~4.
2, mould proof antibacterial ultraviolet film according to claim 1 is characterized in that it also comprises aerosil 0.1~2 weight part.
3, mould proof antibacterial ultraviolet film according to claim 1 and 2 is characterized in that its described thinner is the mixture of epoxy chloropropane-vinylformic acid or tripropylene glycol diacrylate or tri methylol triacrylate or epoxy chloropropane-vinylformic acid and tripropylene glycol diacrylate or mixture or the mixture of tripropylene glycol diacrylate and tri methylol triacrylate or the mixture of epoxy chloropropane-vinylformic acid and tripropylene glycol diacrylate and tri methylol triacrylate of epoxy chloropropane-vinylformic acid and tri methylol triacrylate.
4, the preparation method of the described mould proof antibacterial ultraviolet film of a kind of claim 1, it is characterized in that by described weight part thinner and epoxy acrylic resin, benzophenone, 2,2-dimethoxy-1,2-phenylbenzene ethyl ketone, trolamine, mix, add silver-colored zine ion sterilant again, stir and make finished product.
5, the preparation method of mould proof antibacterial ultraviolet film according to claim 4 is characterized in that the aerosil that also adds 0.1~2 weight part mixes.
CNB2005100479318A 2005-12-07 2005-12-07 Mould proof antibacterial ultraviolet film and its preparing method Expired - Fee Related CN100357376C (en)

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Publication number Priority date Publication date Assignee Title
CN102944063B (en) * 2012-09-27 2015-06-17 广东万家乐燃气具有限公司 Antibacterial enamel tank for water heater and production method thereof
CN104110844A (en) * 2013-09-04 2014-10-22 芜湖美的厨卫电器制造有限公司 Inner container of antibacterial water heater, manufacturing method of inner container and antibacterial water heater with the inner container
CN109135603B (en) * 2018-08-02 2023-01-17 江苏双星彩塑新材料股份有限公司 Antibacterial explosion-proof window film

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1552781A (en) * 2003-06-02 2004-12-08 深圳市海川实业股份有限公司 Ultraviolet photocurable anti-static paint

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552781A (en) * 2003-06-02 2004-12-08 深圳市海川实业股份有限公司 Ultraviolet photocurable anti-static paint

Non-Patent Citations (1)

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Title
聚合活性抗静电剂合成及在紫外光固化涂料中的应用 奚惠兰等.上海涂料,第四期 2001 *

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