CN109422893A - A kind of antibacterial film and preparation method - Google Patents
A kind of antibacterial film and preparation method Download PDFInfo
- Publication number
- CN109422893A CN109422893A CN201710790391.5A CN201710790391A CN109422893A CN 109422893 A CN109422893 A CN 109422893A CN 201710790391 A CN201710790391 A CN 201710790391A CN 109422893 A CN109422893 A CN 109422893A
- Authority
- CN
- China
- Prior art keywords
- antibacterial
- film
- parts
- ammonium salt
- quaternary ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
- C08J7/065—Low-molecular-weight organic substances, e.g. absorption of additives in the surface of the article
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- 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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of antibacterial film and preparation methods.Antibacterial film includes the film by sided corona treatment and the antibacterial coating oxidant layer coated on film surface, and long alkyl chain antibacterial coating agent is 0.02~5g/cm in the coated weight of corona film surface2.Wherein, long alkyl chain antibacterial coating agent includes siliceous 100 parts by weight of quaternary ammonium salt of long alkyl chain and water 50-300 parts by weight；The siliceous quaternary ammonium salt of long alkyl chain is to be synthesized by tertiary amine radical siloxane with alkyl halide.Preparation method includes antibacterial coating agent being coated in corona film surface antibacterial film is made.The present invention can realize the modification of the high antibiotic rate of film on traditional simple synthesis device, while antibacterial material does not migrate, health environment-friendly, and obtained antibacterial film has a wide range of applications in packaging field.
Description
Technical field
The present invention relates to anti-biotic material fields, further say, are to be related to one kind to resist based on the siliceous quaternary ammonium salt of long alkyl chain
Bacterium film and preparation method.
Background technique
Bacterium is to cause people's disease important source, invades and harasses people's lives with always carving, their mass propagation
People's health can be threatened.Being constantly progressive and increasingly improved with people's lives level with science and technology, people self
Health perception is constantly reinforced, and the application of anti-biotic material also gradually attracts people's attention.People are first in daily life
Touching all is panoramic a variety of materials, such as daily necessities, food packaging, amenities, household electrical appliance, public utility
Deng, the handrail encountered when taking bus, the button encountered when taking elevator all becomes the field of bacterial reproduction, propagation
Institute.Spread of germs in order to prevent reduces cross-infection, should advocate and carry out referring to that using antimicrobial product in social public place
It is promoted the well-being of mankind a bit with antibacterial and bactericidal property functional material with improving health of people level.
Broadly, antibacterial functions mainly include the multiple-microorganisms such as antibacterium, mould, fungi even virus, i.e., " anti-
Microorganism ", and the saying of narrow sense just refers to " antibacterium ".Excellent anti-biotic material should have following biomaterials: no
Only have outside apparent antibacterial effect to pathogenic microorganisms, to be also able to maintain anti-microbial property and reach enough use time materials
Material cannot release noxious material, and should be had using the anti-biotic material for capableing of green reclaim membranous type after useful life is reached
Good intensity also to have certain flexible material can itself clean, application conditions are simple, it is desirable to convenient for degradation
Recycle function.
The breeding of bacterium seriously affects the health of the mankind, inorganic metal such as Ag+Although having antibiotic property, dispersed
It can migrate in the material, so that the antibacterial effect of material is not lasting, and will cause environmental pollution.Antibacterial agent is divided into nothing
Machine and organic antibacterial agent.Inorganic antiseptic has Ag+、Cu2+、Zn2+, anti-biotic material can be prepared by being dispersed in material.But when
Between it is too long antibacterial agent will be caused to migrate, not only result in environmental pollution, and antibacterial effect cannot be lasting.It is added into
In plastic products, overlong time product color can change, influence using.Organic antibacterial agent has acid, ester, alcohol, phenol, quaternary ammonium
The small molecules such as salt, this micromolecular, which is added into material, can also migrate, and toxicity is big, greatly limit
It is used.Antibacterial agent described above belongs to release type.
Mainly high molecular quaternary is chemically bonded in material in the prior art, is not migrated, durable antibacterial effect,
Belong to contact-type antibacterial, however quaternary ammonium salt monomer has positive charge, it is mutually exclusive, it not easily passs through direct homopolymerization and obtains macromolecule
The polymer [103232587 A of CN] of amount.Research at present, which is concentrated mainly on, keeps the smallest feelings of quaternary ammonium salt antiseptic additive amount
Under condition, efficient anti-microbial property is obtained.Make now with a kind of novel fluorine quaternary ammonium salt antiseptic since the surface of fluorine can be smaller
Obtaining quaternary ammonium salt can utmostly be enriched on the surface of the material, to obtain excellent anti-microbial property.But fluorine-containing quaternary ammonium salt cost compared with
Height, and fluorine is larger to environmental and human health impacts injury, therefore [Zhao J cannot be widely used；Millians W.Self-
stratified antimicrobial acrylic coatings via one-step UV curing.J.ACS
applied materials&interfaces 2015, 7(33):18467-18472].Not fluorine-containing quaternary ammonium salt in the prior art
Mostly small molecule quaternary ammonium salt or short-chain branch quaternary ammonium salt, but it can not be diffused into cell wall and penetrating cell wall, it cannot be with cell membrane
In conjunction with and destroy membrane structure, cause antibacterial effect bad and easy to migrate.
Summary of the invention
To solve the problem in the prior art, the present invention provides a kind of based on the siliceous quaternary ammonium salt of long alkyl chain
Antibacterial film and preparation method.Present invention introduces have long alkyl chain siliceous quaternary ammonium salt, can by with corona film surface
Hydrolysis-condensation reaction occurs for hydroxyl, and siliceous quaternary ammonium salt is directly bonded to effectively improve the anti-microbial property of material in film surface,
Achieve the purpose that contact-type antibacterial.
An object of the present invention is to provide a kind of antibacterial film.
The antibacterial film includes that the film by sided corona treatment and the antibacterial coated on film surface coat oxidant layer,
Wherein, the antibacterial coating agent by include following components raw material be made, each component according to parts by weight:
Siliceous 100 parts by weight of quaternary ammonium salt of long alkyl chain；
Water 50-300 parts by weight；
The coated weight of the antibacterial coating agent is 0.02~5g/cm2, preferably 0.1~3g/cm2。
The film is polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyimides, the polyamides that sided corona treatment is crossed
At least one of amine, polyvinyl alcohol, polyester, polyphenylene oxide, polyurethane, polyacrylonitrile film；Sided corona treatment uses the prior art
In common processing method.
The siliceous quaternary ammonium salt of long alkyl chain is to be synthesized by tertiary amine radical siloxane with alkyl halide, and raw material is by weight
Number meter, including following components:
The tertiary amine radical siloxane are as follows:
Wherein R, R1、R5Selected from C1-C6 alkyl (CmH2m), C1-C6 alkoxy (CmH2m- O), phenyl (CmHm-2), m 1-
6；Wherein R2、R3、R4Selected from C1-C6 alkyl (CiH2i), i 1-6；
The polymerization inhibitor is p-hydroxyanisole, hydroquinone, 1,4-benzoquinone, hydroquinone methyl ether, 2- tert-butyl to benzene
At least one of diphenol；
The solvent is at least one of acetonitrile, acetone, ethyl acetate, toluene；
The alkyl halide is chloro octane, bromooctane, iodo octane, chloro nonane, bromo nonane, iodo nonane, chlorine
For decane, bromodecane, iodo decane, chloro hendecane, bromoundecane, iodo hendecane, chlorinated dodecane, bromo ten
At least one of dioxane, dodecyl iodides.
The siliceous quaternary ammonium salt of long alkyl chain can be prepared according to usual way in the prior art, the present invention preferably according to
Method comprising the following steps preparation:
(1) solvent is added in tertiary amine radical siloxane and alkyl halide and obtains mixed solution, polymerization inhibitor is then added, in 30-45
8-12h is reacted at DEG C；
(2) solution that reaction obtains is rotated into 1-2h at 50 DEG C -70 DEG C, after removing unreacted alkyl halide and solvent
Obtain orange quaternary ammonium salt liquid.
The present invention can also add micro additive in the antibacterial film according to the actual situation, such as colorant,
Processing aid etc., dosage are conventional amount used, or requirement according to the actual situation is adjusted, and will not influence the film
Basic performance.
The second object of the present invention is to provide a kind of preparation method of antibacterial film.
The antibacterial film is prepared according to the following steps:
(1) the siliceous quaternary ammonium salt of long alkyl chain is dispersed in water to obtain antibacterial coating agent；
(2) antibacterial coating agent is coated uniformly on corona film surface by the dosage, the antibacterial film is made.
Antibacterial film provided by the invention, the polypropylene that the siliceous quaternary ammonium salt of long alkyl chain is crossed applied to sided corona treatment gather
Ethylene, polyvinyl chloride, polystyrene, polyimides, polyamide, polyvinyl alcohol, polyester, polyphenylene oxide, polyurethane, polyacrylonitrile
At least one of film, obtained film safety and environmental protection, anti-microbial property high-efficient and lasting.
The quaternary ammonium salt with Long carbon chain, which is introduced, in material makes it have very strong anti-microbial property.Its Antibacterial Mechanism include with
Under several steps: 1, negatively charged bacterial adsorption is diffused into cell wall to its surface 2, long alkyl chain by positively charged quaternary ammonium salt
And it penetrating cell wall 3, in conjunction with cell membrane and destroys membrane structure 4, cause potassium ion, the deoxyribose core in cell membrane
The leakage 5 of the substances such as acid, ribonucleic acid, bacterial cell death.The antibacterial composite wood of quaternary ammonium salt long alkyl chain is introduced with covalent bond
Expect anti-microbial property with higher, and will not migrate, use is safe, can be applicable to the every field such as food packaging.
The present invention uses the siliceous quaternary ammonium salt of Long carbon chain, the silicon oxygen bond in the siliceous quaternary ammonium salt of long alkyl chain can at corona
Hydroxyl reaction on the film surface managed, makes Long carbon chain in film surface by covalent bond keyed for long alkyl chain quaternary ammonium salt
Quaternary ammonium salt can be utmostly enriched in film surface, do not migrated, belonged to contact-type antibacterial.The peace of antibacterial agent used in the present invention
Loopful is protected, and anti-microbial property high-efficient and lasting can all have very big application prospect in fields such as food, packaging and medical instruments.
The siliceous quaternary ammonium salt antibacterial film of a kind of long alkyl chain provided by the invention can be on traditional simple synthesis device
Realize the modification of the high antibiotic rate of film, while antibacterial material does not migrate, health environment-friendly, has a wide range of applications in packaging field.
In order to measure the anti-microbial property of material, antibiotic rate detection is carried out to film.The preparation method provided according to the present invention
The siliceous quaternary ammonium salt antibacterial film of long alkyl chain obtained has high antibiotic rate, antibacterial timeliness length, intensity height, toughness high, anti-
The features such as fungus matter does not migrate.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
By [the synthesis chemistry of unsaturated quaternary ammonium salt and bonding, 1997 (3): 128-130.] published method, self-control is different
The siliceous quaternary ammonium salt of long alkyl chains.
Embodiment 1
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 120 parts of bromooctane (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 200 parts of acetonitriles, and 30 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 1,
Structural formula such as following formula:
By 100 partsSiliceous quaternary ammonium salt 1It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 1.By 20 partsAntibacterial coating agent 1
Coated in 5*5cm2Corona polypropylene film on (coated weight 0.53g/cm2), it is preparedAntibacterial polypropylene film 1.And
Antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
Embodiment 2
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 150 parts of bromodecane (we
Fourth), 0.125 part of 2- tert-butyl hydroquinone (Aladdin) is added in 250 parts of ethyl acetate, and 35 DEG C of reaction 10h are preparedContain Silicon quaternary ammonium salt 2, structural formula such as following formula:
By 100 partsSiliceous quaternary ammonium salt 2It is dispersed in 100 parts of water and is preparedAntibacterial coating agent 2.By 30 partsAntibacterial coating Agent 2Coated in 5*5cm2Corona polypropylene film on (coated weight 0.6g/cm2), it is preparedAntibacterial polypropylene film 2。
And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
Embodiment 3
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 250 parts of bromododecanes (Ah
Latin), 0.15 part of p-hydroxyanisole (Aladdin) is added in 300 parts of acetone, and 45 DEG C of reaction 10h are preparedSiliceous quaternary ammonium Salt 3, structural formula such as following formula:
By 100 partsSiliceous quaternary ammonium salt 3It is dispersed in 300 parts of water and is preparedAntibacterial coating agent 3.By 40 partsAntibacterial coating Agent 3Coated in 5*5cm2Corona polypropylene film on (coated weight 0.4g/cm2), it is preparedAntibacterial polypropylene film 3。
And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
Comparative example 1
By commercially available corona polypropylene film (PP, Shunde District, Foshan City close innovation and be full of packaging material), it is cut into 5*5cm2Sample
Piece, according to associated test standards, antibiotic rate test result is included in table 1.
Comparative example 2
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 150 parts of bromic ether (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 350 parts of acetonitriles, and 30 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 4,
Structural formula such as following formula:
By 100 partsSiliceous quaternary ammonium salt 4It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 4.By 10 partsAntibacterial coating agent 4
Coated in 5*5cm2Corona polypropylene film on (coated weight 0.26g/cm2), it is preparedAntibacterial polypropylene film 4.And
Antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
Comparative example 3
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 150 parts of bromo pentane (we
Fourth), 0.12 part of p-hydroxyanisole (Aladdin) is added in 200 parts of ethyl acetate, and 40 DEG C of reaction 8h are preparedSiliceous quaternary ammonium Salt 5, structural formula such as following formula:
By 100 partsSiliceous quaternary ammonium salt 5It is dispersed in 200 parts of water and is preparedAntibacterial coating agent 5.By 10 partsAntibacterial coating Agent 5Coated in 5*5cm2Corona polypropylene film on (coated weight 0.13g/cm2), it is preparedAntibacterial polypropylene film 5。
And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
Comparative example 4
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 200 parts of heptane bromide (we
Fourth), 0.125 part of p-hydroxyanisole (Aladdin) is added in 250 parts of ethyl acetate, and 40 DEG C of reaction 10h are preparedSiliceous season Ammonium salt 6, structural formula such as following formula:
By 100 partsSiliceous quaternary ammonium salt 6It is dispersed in 300 parts of water and is preparedAntibacterial coating agent 6.By 30 partsAntibacterial coating Agent 6Coated in 5*5cm2Corona polypropylene film on (coated weight 0.3g/cm2), it is preparedAntibacterial polypropylene film 6。
And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
The antibiotic rate of table 1 embodiment and comparative example
| Antibiotic rate (%) | |
| Embodiment 1 | 52 |
| Embodiment 2 | 92 |
| Embodiment 3 | 100 |
| Comparative example 1 | 0 |
| Comparative example 2 | 0 |
| Comparative example 3 | 0 |
| Comparative example 4 | 0 |
From in the performance test data of above-described embodiment 1~3 and comparative example 1~4, it can analyze and obtain: is uncoated siliceous
The antibiotic rate of the corona polypropylene film of quaternary ammonium salt is zero；When the carbon atom number of alkyl chain in siliceous quaternary ammonium salt is less than 8,
Polypropylene film is substantially without antibiotic property；When the carbon atom number of alkyl chain is 8-12, polyurethane film anti-microbial property is excellent.
Embodiment 4
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 200 parts of bromooctane (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 300 parts of ethyl acetate, and 40 DEG C of reaction 10h are preparedSiliceous quaternary ammonium Salt 7。
By 100 partsSiliceous quaternary ammonium salt 7It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 7.By 10 partsAntibacterial coating agent 7
Coated in 5*5cm2Corona polyethylene film on (coated weight 0.26g/cm2), it is preparedAntimicrobial polyethylene film 1.And
Antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 2.
Embodiment 5
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 170 parts of bromodecane (we
Fourth), 0.15 part of p-hydroxyanisole (Aladdin) is added in 350 parts of acetonitriles, and 30 DEG C of reaction 12h are preparedSiliceous quaternary ammonium salt 8。
By 100 partsSiliceous quaternary ammonium salt 8It is dispersed in 100 parts of water and is preparedAntibacterial coating agent 8.By 20 partsAntibacterial coating Agent 8Coated in 5*5cm2Corona polyethylene film on (coated weight 0.4g/cm2), it is preparedAntimicrobial polyethylene film 2。
And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 2.
Embodiment 6
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 175 parts of bromododecanes (Ah
Latin), 0.125 part of p-hydroxyanisole (Aladdin) is added in 200 parts of ethyl acetate, and 40 DEG C of reaction 12h are preparedIt is siliceous Quaternary ammonium salt 9。
By 100 partsSiliceous quaternary ammonium salt 9It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 9.By 80 partsAntibacterial coating agent 9
Coated in 5*5cm2Corona polyethylene film on (coated weight 2.13g/cm2), it is preparedAntimicrobial polyethylene film 3.And
Antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 2.
Comparative example 5
By commercially available corona polyethylene film (PE, come packaging material for Changshu City), it is cut into 5*5cm2Print, according to phase
Testing standard is closed, antibiotic rate test result is included in table 2.
Comparative example 6
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 125 parts of bromic ether (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 250 parts of ethyl acetate, and 40 DEG C of reaction 10h are preparedSiliceous quaternary ammonium Salt 10。
By 100 partsSiliceous quaternary ammonium salt 10It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 10.By 40 partsAntibacterial coating Agent 10Coated in 5*5cm2Corona polyethylene film on (coated weight 1g/cm2), it is preparedAntimicrobial polyethylene film 4.And
Antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 2.
Comparative example 7
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 175 parts of bromo propane (we
Fourth), 0.125 part of p-hydroxyanisole (Aladdin) is added in 300 parts of ethyl acetate, and 30 DEG C of reaction 10h are preparedSiliceous season Ammonium salt 11。
By 100 partsSiliceous quaternary ammonium salt 11It is dispersed in 100 parts of water and is preparedAntibacterial coating agent 11.By 20 partsAntibacterial applies Cover agent 11Coated in 5*5cm2Corona polyethylene film on (coated weight 0.4g/cm2), it is preparedAntimicrobial polyethylene film 5.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 2.
Comparative example 8
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 200 parts of bromo hexane (we
Fourth), 0.12 part of p-hydroxyanisole (Aladdin) is added in 350 parts of ethyl acetate, and 40 DEG C of reaction 10h are preparedSiliceous season Ammonium salt 12。
By 100 partsSiliceous quaternary ammonium salt 12It is dispersed in 300 parts of water and is preparedAntibacterial coating agent 12.By 20 partsAntibacterial applies Cover agent 12Coated in 5*5cm2Corona polyethylene film on (coated weight 0.2g/cm2), it is preparedAntimicrobial polyethylene film 6.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 2.
The antibiotic rate of table 2 embodiment and comparative example
| Antibiotic rate (%) | |
| Embodiment 4 | 56 |
| Embodiment 5 | 98 |
| Embodiment 6 | 100 |
| Comparative example 5 | 0 |
| Comparative example 6 | 0 |
| Comparative example 7 | 0 |
| Comparative example 8 | 0 |
From in the performance test data of above-described embodiment 4~6 and comparative example 5~8, it can analyze and obtain: is uncoated siliceous
The polyethylene film antibiotic rate of quaternary ammonium salt is zero；When long alkyl chains are greater than 8 carbon in the siliceous QAS polymer of long alkyl chain
Atomic time, the polyethylene film anti-microbial property coated is excellent, and as the increase anti-microbial property of long alkyl chains increases
By force.
Embodiment 7
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 250 parts of bromodecane (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 200 parts of acetone, and 35 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 13。
By 100 partsSiliceous quaternary ammonium salt 13It is dispersed in 300 parts of water and is preparedAntibacterial coating agent 13.By 40 partsAntibacterial applies Cover agent 13Coated in 5*5cm2Corona polyvinyl chloride film on (coated weight 0.4g/cm2), it is preparedAntibacterial polyvinyl chloride Film 1.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 3.
Embodiment 8
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 175 parts of bromododecanes (Ah
Latin), 0.125 part of p-hydroxyanisole (Aladdin) is added in 250 parts of acetone, and 40 DEG C of reaction 10h are preparedSiliceous quaternary ammonium Salt 14。
By 100 partsSiliceous quaternary ammonium salt 14It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 14.By 60 partsAntibacterial coating Agent 14Coated in 5*5cm2Corona polyvinyl chloride film on (coated weight 1.6g/cm2), it is preparedAntibacterial polyvinyl chloride is thin Film 2.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 3.
Comparative example 9
By commercially available corona polyvinyl chloride film (PVC, the permanent nanometer new material in Zibo day), it is cut into 5*5cm2Print, according to
Associated test standards, antibiotic rate test result are included in table 3.
Comparative example 10
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 150 parts of butyl bromide (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 300 parts of acetone, and 45 DEG C of reaction 12h are preparedSiliceous quaternary ammonium salt 15。
By 100 partsSiliceous quaternary ammonium salt 15It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 15.By 30 partsAntibacterial coating Agent 15Coated in 5*5cm2Corona polyvinyl chloride film on (coated weight 0.8g/cm2), it is preparedAntibacterial polyvinyl chloride is thin Film 3.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 3.
The antibiotic rate of table 3 embodiment and comparative example
| Antibiotic rate (%) | |
| Embodiment 7 | 92 |
| Embodiment 8 | 100 |
| Comparative example 9 | 0 |
| Comparative example 10 | 0 |
From in the performance test data of above-described embodiment 7~8 and comparative example 9~10, it can analyze and obtain: is uncoated anti-
The antibiotic rate of the polyvinyl chloride film of bacterium coating agent is zero, and the polyvinyl chloride antibiotic rate for coating short alkyl chain antibacterial coating agent is
Zero；With the increase of long alkyl chains, polyvinyl chloride film in polyvinyl chloride film coated with the siliceous quaternary ammonium salt of long alkyl chain
Anti-microbial property enhancing.
Embodiment 9
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 175 parts of bromodecane (we
Fourth), 0.125 part of p-hydroxyanisole (Aladdin) is added in 350 parts of acetone, and 35 DEG C of reaction 10h are preparedSiliceous quaternary ammonium salt 16。
By 100 partsSiliceous quaternary ammonium salt 16It is dispersed in 100 parts of water and is preparedAntibacterial coating agent 16.By 10 partsAntibacterial applies Cover agent 16Coated in 5*5cm2Corona polystyrene film on (coated weight 0.2g/cm2), it is preparedAntibacterial polystyrene Film 1.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 4.
Embodiment 10
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 250 parts of bromododecanes (Ah
Latin), 0.15 part of p-hydroxyanisole (Aladdin) is added in 200 parts of acetonitriles, and 30 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 17。
By 100 partsSiliceous quaternary ammonium salt 17It is dispersed in 200 parts of water and is preparedAntibacterial coating agent 17.By 20 partsAntibacterial applies Cover agent 17Coated in 5*5cm2Corona polystyrene film on (coated weight 0.26g/cm2), it is preparedAntibacterial polyphenyl second Alkene film 2.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 4.
Comparative example 11
By commercially available corona polystyrene film (PS founds modeling packaging material), it is cut into 5*5cm2Print, according to correlative measurement
Test-object is quasi-, and antibiotic rate test result is included in table 4.
Comparative example 12
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 200 parts of bromo pentane (we
Fourth), 0.12 part of p-hydroxyanisole (Aladdin) is added in 250 parts of acetone, and 35 DEG C of reaction 10h are preparedSiliceous quaternary ammonium salt 18。
By 100 partsSiliceous quaternary ammonium salt 18It is dispersed in 100 parts of water and is preparedAntibacterial coating agent 18.By 70 partsAntibacterial applies Cover agent 18Coated in 5*5cm2Corona polystyrene film on (coated weight 1.4g/cm2), it is preparedAntibacterial polystyrene Film 3.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 4.
The antibiotic rate of table 4 embodiment and comparative example
| Antibiotic rate (%) | |
| Embodiment 9 | 71 |
| Embodiment 10 | 100 |
| Comparative example 11 | 0 |
| Comparative example 12 | 0 |
From in the performance test data of above-described embodiment 9~10 and comparative example 11~12, it can analyze and obtain: is uncoated
The antibiotic rate of the polystyrene film of antibacterial coating agent is zero, coats the polystyrene antibiotic rate of short alkyl chain antibacterial coating agent
It is zero；With the increase of long alkyl chains in polystyrene film coated with the siliceous quaternary ammonium salt of long alkyl chain, polystyrene is thin
The enhancing of film anti-microbial property.
Embodiment 11
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 120 parts of bromodecane (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 300 parts of acetone, and 45 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 19。
By 100 partsSiliceous quaternary ammonium salt 19It is dispersed in 50 parts of water and is preparedAntibacterial coating agent 19.By 30 partsAntibacterial coating Agent 19Coated in 5*5cm2Corona Kapton on (coated weight 0.8g/cm2), it is preparedAntibacterial polyimides is thin Film 1.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 5.
Embodiment 12
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 120 parts of bromodecane (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 350 parts of acetone, and 30 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 20。
By 100 partsSiliceous quaternary ammonium salt 20It is dispersed in 100 parts of water and is preparedAntibacterial coating agent 20.By 20 partsAntibacterial applies Cover agent 20Coated in 5*5cm2Corona Kapton on (coated weight 0.4g/cm2), it is preparedAntibacterial polyimides Film 2.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 5.
Comparative example 13
By commercially available corona Kapton (PI founds modeling packaging material), it is cut into 5*5cm2Print, according to correlative measurement
Test-object is quasi-, and antibiotic rate test result is included in table 5.
The antibiotic rate of table 5 embodiment and comparative example
| Antibiotic rate (%) | |
| Embodiment 11 | 95 |
| Embodiment 12 | 87 |
| Comparative example 13 | 0 |
From in the performance test data of above-described embodiment 11~12 and comparative example 13, it can analyze and obtain: uncoated antibacterial
The antibiotic rate of the Kapton of coating agent is zero；In Kapton coated with the siliceous quaternary ammonium salt of long alkyl chain with
The increase of siliceous quaternary ammonium salt content in antibacterial coating agent, Kapton anti-microbial property enhancing.
Embodiment 13
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 150 parts of bromodecane (we
Fourth), 0.1 part of p-hydroxyanisole (Aladdin) is added in 200 parts of acetone, and 30 DEG C of reaction 8h are preparedSiliceous quaternary ammonium salt 21。
By 100 partsSiliceous quaternary ammonium salt 21It is dispersed in 150 parts of water and is preparedAntibacterial coating agent 21.By 20 partsAntibacterial applies Cover agent 21Coated in 5*5cm2Corona polyamide film on (coated weight 0.32g/cm2), it is preparedAntibacterial polyamide is thin Film 1.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 6.
Embodiment 14
By 100 parts of diethylin for methyltriethoxysilane (Nanjing sieve grace silicon materials), 200 parts of bromododecanes (Ah
Latin), 0.125 part of p-hydroxyanisole (Aladdin) is added in 250 parts of ethyl acetate, and 40 DEG C of reaction 8h are preparedIt is siliceous Quaternary ammonium salt 22。
By 100 partsSiliceous quaternary ammonium salt 22It is dispersed in 200 parts of water and is preparedAntibacterial coating agent 22.By 30 partsAntibacterial applies Cover agent 22Coated in 5*5cm2Corona polyamide film on (coated weight 0.4g/cm2), it is preparedAntibacterial polyamide film 2.And antibacterial test is carried out according to relevant criterion, antibiotic rate test result is included in table 1.
Comparative example 14
By commercially available corona polyamide film (PA founds modeling packaging material), it is cut into 5*5cm2Print, according to dependence test
Standard, antibiotic rate test result are included in table 1.
The antibiotic rate of table 6 embodiment and comparative example
| Antibiotic rate (%) | |
| Embodiment 13 | 87 |
| Embodiment 14 | 100 |
| Comparative example 14 | 0 |
From in the performance test data of above-described embodiment 13~14 and comparative example 14, it can analyze and obtain: uncoated antibacterial
The antibiotic rate of the polyamide film of coating agent is zero；With alkane in polyamide film coated with the siliceous quaternary ammonium salt of long alkyl chain
The increase of base chain length, the enhancing of polyamide film anti-microbial property.
Antibacterial film provided by the invention based on siliceous quaternary ammonium salt can be directly used for the preparation of conventional polymer forming method
The antimicrobial product that difference requires.In addition, micro or a small amount of additive, such as processing aid, colorant, anti-hydrolysis agent etc. will not
The anti-microbial property of antibacterial film described in shadow.
It should be understood by those ordinary skilled in the art that: the above is only a specific embodiment of the present invention, and
It is not used in the limitation present invention, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done,
It should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of antibacterial film, it is characterised in that the antibacterial film includes film by sided corona treatment and is coated on film table
The antibacterial in face coats oxidant layer,
Wherein, the antibacterial coating agent by include following components raw material be made, each component according to parts by weight:
Siliceous 100 parts by weight of quaternary ammonium salt of long alkyl chain；
Water 50-300 parts by weight；
The coated weight of the antibacterial coating agent is 0.02~5g/cm2。
2. antibacterial film as described in claim 1, it is characterised in that:
The film be polypropylene, polyethylene, polyvinyl chloride, polystyrene, polyimides, polyamide, polyvinyl alcohol, polyester,
At least one of polyphenylene oxide, polyurethane, polyacrylonitrile film.
3. antibacterial film as described in claim 1, it is characterised in that:
The coated weight of the antibacterial coating agent is 0.1~3g/cm2。
4. antibacterial film as described in claim 1, it is characterised in that: the siliceous quaternary ammonium salt of long alkyl chain is by tertiary amine groups silicon oxygen
Alkane is synthesized into alkyl halide, each component according to parts by weight:
Wherein, the tertiary amine radical siloxane are as follows:
R、R1、R5Selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl；R2、R3、R4Selected from C1-C6 alkyl；
The polymerization inhibitor is p-hydroxyanisole, hydroquinone, 1,4-benzoquinone, hydroquinone methyl ether, 2- tert-butyl hydroquinone
At least one of；
The solvent is at least one of acetonitrile, acetone, ethyl acetate, toluene；
The alkyl halide is chloro octane, bromooctane, iodo octane, chloro nonane, bromo nonane, iodo nonane, the chloro last of the ten Heavenly stems
Alkane, bromodecane, iodo decane, chloro hendecane, bromoundecane, iodo hendecane, chlorinated dodecane, bromododecane,
At least one of dodecyl iodides.
5. antibacterial film as claimed in claim 4, it is characterised in that:
The siliceous quaternary ammonium salt of long alkyl chain is prepared according to method comprising the following steps:
(1) solvent is added in tertiary amine radical siloxane and alkyl halide and obtains mixed solution, polymerization inhibitor is added afterwards, it is anti-at 30-45 DEG C
Answer 8-12h；
(2) solution that reaction obtains is rotated into 1-2h at 50 DEG C -70 DEG C, is grown after removing unreacted alkyl halide and solvent
The siliceous quaternary ammonium salt of alkyl chain.
6. a kind of preparation method of such as described in any item antibacterial films of Claims 1 to 5, it is characterised in that the method packet
It includes:
(1) it is dispersed in water the siliceous quaternary ammonium salt of the long alkyl chain of the dosage to obtain antibacterial coating agent；
(2) antibacterial coating agent is coated uniformly on film surface by the dosage, obtains the antibacterial film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710790391.5A CN109422893A (en) | 2017-09-05 | 2017-09-05 | A kind of antibacterial film and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710790391.5A CN109422893A (en) | 2017-09-05 | 2017-09-05 | A kind of antibacterial film and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109422893A true CN109422893A (en) | 2019-03-05 |
Family
ID=65513495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710790391.5A Pending CN109422893A (en) | 2017-09-05 | 2017-09-05 | A kind of antibacterial film and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109422893A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909411A (en) * | 2020-08-14 | 2020-11-10 | 青岛阳光动力生物医药技术有限公司 | Plastic film with self-disinfection function and preparation method thereof |
| CN113400534A (en) * | 2021-06-18 | 2021-09-17 | 康辉 | Polypropylene film, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102051A (en) * | 1993-10-30 | 1995-05-03 | 南京神奇科技开发有限公司 | Long-acting antimicrobial mildew-retarding agent |
| CN1195298A (en) * | 1995-09-01 | 1998-10-07 | 以色列国农业部 | Method and device for ozone sterilization of objects |
| CN101016310A (en) * | 2007-01-31 | 2007-08-15 | 山东轻工业学院 | Preparing method for organic silicon compound containing quaternary ammonium group |
| CN101812086A (en) * | 2009-11-28 | 2010-08-25 | 深圳大学 | Anti-bacterial compound and preparation method thereof |
-
2017
- 2017-09-05 CN CN201710790391.5A patent/CN109422893A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102051A (en) * | 1993-10-30 | 1995-05-03 | 南京神奇科技开发有限公司 | Long-acting antimicrobial mildew-retarding agent |
| CN1195298A (en) * | 1995-09-01 | 1998-10-07 | 以色列国农业部 | Method and device for ozone sterilization of objects |
| CN101016310A (en) * | 2007-01-31 | 2007-08-15 | 山东轻工业学院 | Preparing method for organic silicon compound containing quaternary ammonium group |
| CN101812086A (en) * | 2009-11-28 | 2010-08-25 | 深圳大学 | Anti-bacterial compound and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TANIA FADIDA ET AL.: ""Air-ozonolysis to generate contact active antimicrobial surfaces:Activation of polyethylene and polystyrene followed by covalent graftof quaternary ammonium salts"", 《COLLOIDS AND SURFACES B: BIOINTERFACES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111909411A (en) * | 2020-08-14 | 2020-11-10 | 青岛阳光动力生物医药技术有限公司 | Plastic film with self-disinfection function and preparation method thereof |
| CN113400534A (en) * | 2021-06-18 | 2021-09-17 | 康辉 | Polypropylene film, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109135232A (en) | A kind of antimicrobial macromolecule composite material and preparation method | |
| CN104140633B (en) | Plastic overmold TPE fire retardant material and preparation method thereof | |
| CN109422893A (en) | A kind of antibacterial film and preparation method | |
| CN110371988A (en) | A kind of preparation method of silica antibacterial microballoon | |
| MX2012011040A (en) | Antimicrobial plastic compositions and methods for preparing same. | |
| CN109694483A (en) | A kind of antibacterial aqueous polyaminoester emulsion and preparation method | |
| WO2004102690A3 (en) | Organic polymers, laminates, and capacitors | |
| JPWO2019159864A1 (en) | Compositions and moldings | |
| KR101976473B1 (en) | Anti-bacterial coating composition | |
| CN105585793B (en) | A kind of PVC mixture with clean surfaces function and preparation method thereof | |
| CN104804558A (en) | Antibacterial powder coating for pipeline | |
| CN108034295A (en) | A kind of inorganic environment-friendly interior wall mould proof antibacterial paint | |
| CN103923267A (en) | Polyester-modified acrylic resin with antibacterial function and preparation method thereof | |
| KR102128282B1 (en) | Anti-bacterial and anti-fouling coating composition, film using the same, method of the same and coated product | |
| Tu et al. | Antibacterial properties of poly (dimethylsiloxane) surfaces modified with graphene oxide-catechol composite | |
| CA2549861A1 (en) | Biocidal siloxane coating material containing n-halogenated amine and amide functional groups | |
| JPWO2019159865A1 (en) | Mold | |
| CN105062314B (en) | A kind of high-low temperature resistant UV plastic coatings and preparation method thereof | |
| Kim et al. | Allylimidazolium salt based antibacterial polymer coatings produced by thiol–ene photocuring | |
| CN103554367A (en) | Beta-cyclodextrin containing halogen amine antimicrobial agent copolymer as well as preparation method and application of copolymer | |
| CN101679779B (en) | Substrates with biopassive coating | |
| CN106397920A (en) | Antistatic master batch and preparation method thereof | |
| CN111217956A (en) | Preparation method of cationic custard apple-shaped acrylate copolymer antibacterial microspheres | |
| CN107501476B (en) | A kind of preparation method of photo-crosslinking antibiotic property composite membrane of polyvinyl alcohol | |
| CN111635680B (en) | Water-based material composition, preparation method, application and protective tool |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190305 |
|
| RJ01 | Rejection of invention patent application after publication |