CN114231136A - Antibacterial AG coating liquid composition, antibacterial AG coating liquid, antibacterial AG writing film and preparation method thereof - Google Patents
Antibacterial AG coating liquid composition, antibacterial AG coating liquid, antibacterial AG writing film and preparation method thereof Download PDFInfo
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/06—Unsaturated polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Abstract
The invention provides an antibacterial AG coating liquid composition, which comprises an acrylic prepolymer, an acrylate monomer and a functional factor; wherein, relative to 100 weight parts of functional factors, the content of the acrylic prepolymer is 50-600 weight parts, and the content of the acrylate monomers is 30-300 weight parts; the functional factor is an organic modified inorganic metal oxide. The antibacterial AG writing film prepared from the antibacterial AG coating liquid composition has an anti-dazzle function and a good antibacterial effect.
Description
Technical Field
The invention relates to the technical field of anti-glare film materials, in particular to an antibacterial AG coating liquid composition, an antibacterial AG coating liquid obtained from the antibacterial AG coating liquid composition, an antibacterial AG writing film and a preparation method thereof.
Background
The AG (anti-glare) writing film (AG film for short) is used as a protective film of a writing screen, a display screen, a touch screen and the like, and has good performances of anti-dazzle, anti-fatigue, high light transmission, anti-fouling, scratch resistance and the like. Under the current situation of global epidemic situation flooding, the AG writing film is used as a protective film of a writing screen and a touch screen, has antibacterial property which is always required by daily life of people, and can effectively inhibit viruses and avoid cross infection if the AG film has antibacterial property. At present, the realization mode of the AG writing film antibiosis is mainly based on an antibacterial agent additive type. Two conventional ways are: one is obtained by mixing an organic antibacterial agent and AG particles and then coating; the other is obtained by mixing a metal ion antibacterial agent and AG particles and then coating.
However, the antibacterial performance realized by the current additive antibacterial agent in the AG writing film has the following defects: 1. the organic antibacterial agent has toxicity, no high temperature resistance and poor antibacterial long-term effect, and the dispersion of AG particles is influenced by adding more of the organic antibacterial agent, so that the coating appearance is poor. 2. On one hand, the metal ion type antibacterial agent is adopted, the bad crystal point caused by sedimentation is considered, and meanwhile, in order to achieve the ideal antibacterial performance, a large proportion amount of the metal ion type antibacterial agent is required to be added, so that the cost is increased.
Therefore, it is important to develop an AG writing film having excellent antibacterial properties without adding an antibacterial agent.
Disclosure of Invention
An object of the present invention is to overcome the above-mentioned problems of the prior art and to provide an antibacterial AG coating liquid composition, an antibacterial AG coating liquid obtained from the antibacterial AG coating liquid composition, an antibacterial AG writing film, and a method for producing the antibacterial AG writing film. The antibacterial AG writing film does not contain an added antibacterial agent and has good antibacterial performance.
In order to achieve the above object, the present invention provides in a first aspect an antibacterial AG coating liquid composition comprising an acrylic prepolymer, an acrylate monomer, a functional factor; wherein, relative to 100 weight parts of functional factors, the content of the acrylic prepolymer is 50-600 weight parts, and the content of the acrylate monomers is 30-300 weight parts;
the functional factor is an organic modified inorganic metal oxide.
The inventor of the invention finds that the antibacterial AG writing film prepared from the antibacterial AG coating liquid composition has an anti-dazzle function and a good antibacterial effect by using the organic modified inorganic metal oxide as AG particles to be matched with the acrylic prepolymer and the acrylate monomer.
According to the invention, the acrylic prepolymer, the acrylate monomer and the functional factor are matched for use, so that the prepared antibacterial AG writing film has a good antibacterial effect, and in order to ensure that the antibacterial effect is better, the proportioning relation of the three components is further optimized. Preferably, the content of the acrylic prepolymer is 300-500 parts by weight and the content of the acrylate monomer is 50-200 parts by weight relative to 100 parts by weight of the functional factor. More preferably, the content of the acrylic prepolymer is 390-410 parts by weight and the content of the acrylate monomer is 90-110 parts by weight relative to 100 parts by weight of the functional factor.
In the present invention, the kind of the inorganic metal oxide is not particularly limited, and an inorganic metal oxide (AG particle) conventionally used in AG writing films in the art may be selected and used in the present invention after being organically modified.
In the invention, the organic modification refers to organic coupling grafting modification, which means that inorganic metal oxide is treated by a coupling agent and then reacts with organic matters for grafting modification.
Preferably, the inorganic metal oxide may be an inorganic metal oxide containing one or more of Ti, Cu, Zn, and Zr metal elements.
Preferably, the inorganic metal oxide is selected from TiO2、CuO、ZnO2And ZrO2One or more of (a).
Preferably, the proportion of inorganic metal oxide in the functional element is from 90 to 98% by weight, preferably from 95 to 98% by weight, based on the total weight of the functional element.
Preferably, the portion of carboxylic acid compounds in the functional factor accounts for 1-5 wt%, preferably 1-3 wt% of the total weight of the functional factor.
In one embodiment of the present invention, the functional factor is prepared by the following method:
(1) first contacting an inorganic metal oxide with a coupling agent;
(2) and (2) carrying out second contact on the material obtained in the step (1) and carboxylic acid compounds.
Wherein, in the step (1), the conditions of the first contact comprise: the temperature is 50-65 ℃, the mixing speed is 50-500rpm/min, and the mixing time is 6-10 h.
Preferably, the coupling agent is selected from a silane coupling agent and/or a titanate coupling agent, preferably a silane coupling agent selected from one or more of KH550, KH560 and KH 792.
Wherein, in the step (2), the conditions of the second contact include: the temperature is 55-65 ℃, the mixing speed is 50-500rpm/min, and the mixing time is 2-5 h.
Preferably, the carboxylic acid compounds are selected from long chain fatty acid compounds, more preferably stearic acid.
The preparation method of the functional factor further comprises the step (3): filtering to remove byproducts, vacuum drying and grinding.
In one embodiment of the present invention, the organic coupling graft-modified inorganic metal oxide is prepared by a method comprising the steps of:
(1) mixing inorganic metal oxide and a solvent, carrying out ultrasonic oscillation, heating to 50-65 ℃, slowly dropwise adding a coupling agent, and stirring and reacting for 6-10h at 50-500rpm/min under the condition of condensation reflux;
(2) adding a long-chain fatty acid compound into the material obtained in the step (1), and continuously stirring and reacting for 2-5h at 50-500 rpm/min;
(3) and (3) cooling the material reacted in the step (2), carrying out solid-liquid separation to remove byproducts, and then carrying out vacuum drying and grinding.
In the present invention, in order to provide better performance to the finally prepared AG writing film, the particle size of the functional factor is preferably 1 μm to 5 μm, more preferably 1 μm to 3 μm.
In the present invention, the term "particle size" refers to the geometric spherical diameter of individual particles rather than to an average value, and when a range is used, it means that the particle sizes of such particles in the same material fall within the range; while the invention allows for some tolerance, i.e. when the particle size of less than 5% of the total number of particles is not within the required range, the requirement is considered to be met. The particle size of the functional factor in the invention is measured by a transmission electron microscope.
In the invention, the acrylic prepolymer is polyfunctional group matrix resin; preferably, the multifunctional base resin is a photocurable resin.
More preferably, the multifunctional base resin is an acrylic resin; the acrylic resin is selected from any one or more of epoxy acrylic resin, polyester acrylic resin and polyurethane acrylic resin.
Wherein the epoxy acrylic resin is selected from a nine-functional epoxy acrylic resin oligomer CNUVE151 NS; the polyester acrylic resin is selected from a nine-functional polyester acrylic resin oligomer CN8201 NS; the polyurethane acrylic resin is selected from nine-functional polyurethane acrylic resin oligomer CN983 NS.
According to the invention, the acrylate monomer is an acrylate monomer or a methacrylate monomer with the functionality not less than 2. Preferably, the acrylate monomer is selected from any one or more of dipentaerythritol hydroxyl pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylene propyl triacrylate, propoxylated glycerol triacrylate, trimethylolpropane ethoxy triacrylate, 1, 6-hexanediol diacrylate, propoxylated glyceryl triacrylate, tripropylene glycol diacrylate, and ethylene glycol diacrylate in combination.
In one embodiment of the present invention, in the antibacterial AG coating liquid composition, the acrylic prepolymer is a polyester acrylic resin, the acrylate monomer is dipentaerythritol hydroxyl pentaacrylate, and the weight ratio of the two is 5: 1
In a preferred embodiment of the present invention, in the antibacterial AG coating liquid composition, the acrylic prepolymer is a combination of a polyester acrylic resin and an epoxy acrylic resin (the weight ratio of the two is 3: 1), the acrylate monomer is a combination of dipentaerythritol hydroxypentaacrylate and dipentaerythritol hexaacrylate (the weight ratio of the two is 1: 1), and the weight ratio of the acrylic prepolymer to the acrylate monomer is 4: 1.
the inventor of the invention finds that the acrylic prepolymer is polyester acrylic resin, the acrylate monomer is dipentaerythritol hydroxyl pentaacrylate which is a specific combination, and the acrylic prepolymer and the acrylate monomer have better effect when being matched with functional factors after being cross-linked and polymerized, so that the antibacterial stability and the antibacterial aging of the antibacterial AG writing film are improved.
In the present invention, the antibacterial AG coating liquid composition further includes an auxiliary. The kind of the assistant is not particularly limited, and may be an assistant commonly used in the art for preparing AG writing films, such as an initiator, a leveling agent, a dispersant, a light stabilizer, an antioxidant.
Preferably, the auxiliaries include a photoinitiator and a leveling agent. In order to make the photoinitiator and the leveling agent exert better effects as an auxiliary agent and reduce waste of the amount of the auxiliary agent, it is preferable that the photoinitiator is contained in an amount of 20 to 150 parts by weight and the leveling agent is contained in an amount of 20 to 150 parts by weight, relative to 100 parts by weight of the AG modified particles.
In the invention, the photoinitiator is a cracking type photoinitiator and/or a photosensitive type photoinitiator.
Wherein the cleavage type photoinitiator is selected from one or more of a photoinitiator 1173, a photoinitiator 184, a photoinitiator 907, a photoinitiator 369, a photoinitiator 1490 and a photoinitiator 1700. The photo-sensitive photoinitiator is selected from the group consisting of photoinitiators 184.
Preferably, the leveling agent is a silicon modified leveling agent, and can be selected from one or more of BYK-333, BYK-307, YK-377, BYK-378, BYK-352, BYK-354 and BYK-358.
In the present invention, the antibacterial AG coating liquid composition further includes an organic solvent; the organic solvent is selected from any one or more of alcohols, ketones, alkanes, esters and ethers.
Preferably, the organic solvent is selected from any one or more of butanone, propylene glycol methyl ether, 4-methyl-2-pentanone, propylene glycol methyl ether acetate, ethyl acetate and butyl acetate, and more preferably a combination of butanone and propylene glycol methyl ether.
In a preferred embodiment of the present invention, the antibacterial AG coating liquid composition includes an acrylic prepolymer, an acrylate monomer, an organic coupling graft-modified inorganic metal oxide, a photoinitiator, a leveling agent, and a solvent.
The invention claimed in a first aspect is a composition in which the individual components may be stored individually or in a mixture of several components. It will be appreciated that solvents may not be included in the composition for convenience of storage, transport and sale. The purchaser may add the solvent by himself or herself at the time of preparing the antibacterial AG coating liquid composition.
In a second aspect, the present invention provides an antibacterial AG coating liquid containing or prepared from the antibacterial AG coating liquid composition according to the first aspect of the present invention.
The antibacterial AG coating liquid according to the second aspect of the present invention can be obtained by simply mixing the composition according to the first aspect.
The invention provides an antibacterial AG writing film in a third aspect, which comprises a base material layer and an antibacterial AG coating coated on the surface of the base material layer; the antibacterial AG coating layer is prepared from the antibacterial AG coating liquid according to the second aspect of the present invention, or is prepared from the antibacterial AG coating liquid composition according to the first aspect of the present invention.
In the present invention, the selection of the material of the substrate layer is not particularly limited, and materials conventionally used as a substrate in the art may be selected, for example, the material of the substrate layer may be selected from any one or more of polyethylene terephthalate (PET), triacetyl cellulose, polyethylene naphthalate, polycarbonate, and polymethyl methacrylate.
In order to make the antibacterial property of the prepared antibacterial AG writing film more stable, the thickness of the antibacterial AG coating layer is preferably 1 μm to 6 μm, more preferably 3 μm to 5 μm.
In the invention, the antibacterial AG writing film also comprises a pretreatment layer arranged between the base material layer and the antibacterial AG coating, wherein the pretreatment layer is also called a precoating layer and is formed by performing chemical substrate treatment on the surface of the base material layer, and the pretreatment layer is used for improving the adhesive force between the base material layer and the antibacterial AG coating.
Preferably, the pretreatment layer is selected from any one or more of polyester, polyurethane and acrylic.
Preferably, the thickness of the pretreatment layer is 0.01 μm to 1 μm.
In a preferred embodiment of the present invention, the antibacterial AG writing film includes three layers from bottom to top: a substrate layer, a pretreatment layer and an antibacterial AG coating.
The fourth aspect of the present invention provides a method for producing the antibacterial AG writing film according to the third aspect of the present invention, which comprises carrying out the following steps using the antibacterial AG coating liquid composition according to the first aspect of the present invention as a raw material:
(i) mixing the antibacterial AG coating liquid composition to obtain an antibacterial AG coating liquid;
(ii) coating the antibacterial AG coating liquid obtained in the step (i) on a substrate layer;
(ii) (iii) drying the substrate layer treated in the step (ii) and curing the AG coating liquid.
And (i) uniformly mixing the acrylic prepolymer, the acrylate monomer, the organic coupling graft modified inorganic metal oxide, the photoinitiator, the leveling agent and the solvent according to a ratio to obtain the antibacterial AG coating liquid.
In order to make the coating liquid of the antibacterial AG coating liquid easier to be coated evenly and improve the antibacterial performance of the antibacterial AG writing film, the step (i) further comprises the step of adjusting the coating liquid of the antibacterial AG coating liquid to have the solid content of 20-40%.
In the step (ii), the coating method of the antibacterial AG coating liquid on the substrate layer is not particularly limited, and a coating method conventional in the art may be used.
In the step (iii), the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 1-10 minutes.
In the step (iii), the curing is preferably ultraviolet irradiation curing, preferably the dose of the ultraviolet is 300-2。
The invention adopts the technical scheme and has the following beneficial effects:
(1) in the antibacterial AG coating liquid composition provided by the invention, the organic modified inorganic metal oxide is used as AG particles to be matched with acrylic prepolymer and acrylate monomer, and the functional factor is embedded in the acrylic resin coating, so that the anti-dazzle performance is ensured, and the antibacterial performance is effectively improved on the exposed surface of the particles.
(2) According to the antibacterial AG writing film provided by the invention, the organic modified inorganic metal oxide is used as AG particles, so that the antibacterial stability and the antibacterial aging of the antibacterial AG writing film are improved, the problem of poor coating is solved, and the production cost is reduced.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Drawings
Fig. 1 is a schematic view showing the structure of the AG writing film provided in example 1.
Detailed Description
Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The invention is described in detail below with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Preparation example 1
A preparation method of an organic coupling graft modified inorganic metal oxide comprises the following steps:
(1) adding 2g of inorganic metal oxide and 75ml of solvent into a 250ml three-neck flask, carrying out ultrasonic oscillation for 30min, heating to 60 ℃, slowly dropwise adding 2% silane coupling agent KH550, and rapidly and mechanically stirring at 300rpm/min for 8h under the condition of condensation reflux;
(2) adding 2% stearic acid into a three-neck flask, keeping the temperature at 60 ℃, continuing stirring at 300rpm/min for reaction for 3 hours, naturally cooling the reaction liquid to room temperature, and then performing suction filtration;
(3) and performing Soxhlet extraction on the obtained filter cake to remove redundant coupling agent, stearic acid and byproducts generated in the reaction process, then drying in vacuum and grinding to obtain the organic coupling graft modified inorganic metal oxide.
Wherein the inorganic metal oxide is titanium dioxide.
In the obtained organic coupling graft modified inorganic metal oxide, the inorganic metal oxide part accounts for 90-95 wt% of the total weight, the stearic acid modified part accounts for 1-3 wt% of the total weight, and the rest content is the silane coupling agent modified part.
Preparation example 2
Reference is made to the process of preparation 1, except that the inorganic metal oxide is copper dioxide.
Preparation example 3
Reference is made to the process of preparation 1, except that an inorganic metal oxide, zinc dioxide.
Preparation example 4
The procedure is as in preparation example 1, except that an inorganic metal oxide zirconium dioxide is used.
In the following examples, the components used are all commercially available analytical grades, unless otherwise specified. 1 part by weight represents 1 g.
Example 1
(one) preparing a composition
Acrylic prepolymer: 40 parts by weight of nine-functional polyester acrylic resin oligomer CN8201 NS;
acrylate monomer: 10 parts of dipentaerythritol hydroxyl pentaacrylate;
functional factors: modified titanium dioxide particles (particle diameter 2 μm, obtained by the method of preparation example, the same shall apply hereinafter), 10 parts by weight;
photoinitiator (2): 184 (manufacturer, basf IRGACURE, germany), 5 parts by weight;
leveling agent: BYK-333 (bike), 5 weight parts;
organic solvent: a mixture of butanone and propylene glycol methyl ether (weight ratio is 1: 1), 30 parts by weight;
(II) preparation of antibacterial AG writing film
(i) Uniformly mixing the antibacterial AG coating liquid composition to obtain an antibacterial AG coating liquid;
(ii) (ii) diluting the antibacterial AG coating liquid obtained in the step (i) to a solid content of 35%, and coating the antibacterial AG coating liquid on a PET substrate (provided by Dongli, model XG7PL 2);
(ii) (iii) drying the substrate layer treated in the step (ii) in a circulating oven at 100 ℃ for 2 minutes, and then performing drying at a dosage of 400mJ/cm2And irradiating by ultraviolet light to obtain the antibacterial AG writing film. Wherein the thickness of the PET substrate is 125 μm, and the thickness of the antibacterial AG coating is 3 μm. The structure of the antibacterial AG writing film is schematically shown in figure 1.
Example 2
(one) preparing a composition
Acrylic prepolymer: nine-functional polyester acrylic resin oligomer CN8201NS, 39 parts by weight;
acrylate monomer: 9 parts of dipentaerythritol hydroxyl pentaacrylate;
functional factors: modified titanium dioxide particles (particle diameter 1.5 μm), 10 parts by weight;
photoinitiator (2): 184 (manufacturer, basf IRGACURE, germany), 5 parts by weight;
leveling agent: BYK-333 (bike), 2.5 weight parts;
organic solvent: a mixture of butanone and propylene glycol methyl ether (weight ratio is 1: 1), 34.5 parts;
(II) preparation of antibacterial AG writing film
(i) Uniformly mixing the antibacterial AG coating liquid composition to obtain an antibacterial AG coating liquid;
(ii) (ii) diluting the antibacterial AG coating liquid obtained in the step (i) to a solid content of 30%, and coating the antibacterial AG coating liquid on a PET substrate (provided by Dongli, model XG7PL 2);
(ii) (iii) drying the substrate layer treated in the step (ii) in a circulating oven at 80 ℃ for 3 minutes, and then performing treatment at a dosage of 500mJ/cm2And irradiating by ultraviolet light to obtain the antibacterial AG writing film. Wherein the thickness of the PET substrate is 125 μm, and the thickness of the antibacterial AG coating is 4 μm.
Example 3
(one) preparing a composition
Acrylic prepolymer: nine-functional polyester acrylic resin oligomer CN8201NS, 41 parts by weight;
acrylate monomer: 11 parts of dipentaerythritol hydroxyl pentaacrylate;
functional factors: modified titanium dioxide particles (particle diameter 3 μm), 10 parts by weight;
photoinitiator (2): 184 (manufacturer, basf IRGACURE, germany), 5 parts by weight;
leveling agent: BYK-333 (bike), 10 weight portions;
organic solvent: 23 parts of a mixture of butanone and propylene glycol methyl ether (the weight ratio is 1: 1);
(II) preparation of antibacterial AG writing film
(i) Uniformly mixing the antibacterial AG coating liquid composition to obtain an antibacterial AG coating liquid;
(ii) (ii) diluting the antibacterial AG coating liquid obtained in the step (i) to a solid content of 25%, and coating the antibacterial AG coating liquid on a PET substrate (provided by Dongli, model XG7PL 2);
(ii) (iii) drying the substrate layer treated in step (ii) in a circulating oven at 110 ℃ for 1.5 minutes, followed by a dose of 300mJ/cm2And irradiating by ultraviolet light to obtain the antibacterial AG writing film. Wherein the thickness of the PET substrate is 125 μm, and the thickness of the antibacterial AG coating is 5 μm.
EXAMPLE 4 group
The present set of examples is provided to illustrate the effect of ingredients and ratios in the antimicrobial AG coating liquid composition.
This set of examples was performed as in example 1, except that the ingredients and the proportions in the composition were varied, respectively, while maintaining the total weight of the composition. Specifically, the method comprises the following steps:
example 4 a: changing the ratio of the acrylic prepolymer to the acrylate monomer to ensure that 50 parts by weight of the acrylic prepolymer and 5 parts by weight of the acrylate monomer are added;
example 4 b: changing the ratio of the acrylic prepolymer to the acrylate monomer to ensure that the acrylic prepolymer accounts for 30 parts by weight and the acrylate monomer accounts for 20 parts by weight;
example 4 c:
acrylic prepolymer: 30 parts by weight of a nine-functional polyester acrylic resin oligomer CN8201 NS; 10 parts by weight of epoxy acrylic resin oligomer CNUVE151 NS;
acrylate monomer: 5 parts by weight of dipentaerythritol hydroxyl pentaacrylate; 5 parts of dipentaerythritol hexaacrylate.
Finally, respectively obtaining the antibacterial AG writing film.
EXAMPLE 5 group
The present set of examples is intended to illustrate the effect of a change in the ingredients in the antimicrobial AG coating liquid composition.
This set of examples was performed as in example 1, except that the ingredients in the compositions were changed separately. Specifically, the method comprises the following steps:
example 5 a: the modified titanium dioxide particles were replaced with the same amount of the modified copper dioxide particles obtained in preparation example 2;
example 5 b: the modified titanium dioxide particles were replaced with the same amount of the modified zinc dioxide particles obtained in preparation example 3;
example 5 c: an equivalent amount of the modified zirconia particles obtained in preparation example 4 in place of the modified titania particles;
finally, respectively obtaining the antibacterial AG writing film.
Comparative example 1
Reference was made to example 1, except that the modified titanium dioxide particles were replaced with equal amounts of ordinary silica particles + silver ion-based antibacterial agent (Tianjin Boyuan B8401). Finally obtaining the AG writing film.
Comparative example 2
Reference was made to example 1, except that the modified titanium dioxide particles were replaced with an equal amount of PMMA particles plus a silver ion-based antibacterial agent (tianjin flatstem B8401). Finally obtaining the AG writing film.
Comparative example 3
Reference is made to example 1, except that an equal amount of unmodified silica particles is substituted for the modified titanium dioxide particles. Finally obtaining the AG writing film.
Comparative example 4
Reference is made to example 1, except that the ratio of the acrylic prepolymer to the acrylic monomer is changed to 3 parts by weight of the acrylic prepolymer and 40 parts by weight of the polyethylene glycol is added to the acrylic monomer, while the total weight of the composition is maintained (the amount of the solvent is changed).
Test example
(1) The haze and transmittance of the AG writing films provided in examples and comparative examples were measured using a WGT-S transmittance/haze meter, and the results are recorded in table 1.
(2) The hardness of the AG writing films provided in examples and comparative examples was measured using a push type pencil hardness tester, and the results are recorded in table 1.
(3) The adhesion of the AG coating on the AG writing films provided in the examples and comparative examples was determined using the Baige test (no drop off after boiling in water for 30 min) with reference to the GB/T9286-.
(4) The abrasion resistance of the AG coating on the AG writing film provided in examples and comparative examples was determined 500 times with reference to GBT 1768-.
(5) Referring to industry standards, the appearance of the AG coating on the AG writing film was observed under a darkroom powerful light, and recorded as OK without striae.
(6) The anti-bacterial performance of the AG writing films provided in examples and comparative examples against Staphylococcus aureus and Escherichia coli was determined with reference to GB/T31402-2015 standard.
TABLE 1
As can be seen from table 1, the antibacterial AG writing film prepared by the present invention has excellent antibacterial performance against staphylococcus aureus and escherichia coli, and the antibacterial effect can reach 99.99% at most, and in addition, the antibacterial AG writing film has the advantages of low haze, high light transmittance, high hardness, strong adhesion, good wear resistance, good appearance, etc., and is very suitable for being used as a protective film for writing screens, display screens, touch screens, etc.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and the like that are within the spirit and principle of the present invention are included in the present invention.
Claims (10)
1. An antibacterial AG coating liquid composition is characterized by comprising an acrylic prepolymer, an acrylate monomer and a functional factor; wherein, relative to 100 weight parts of functional factors, the content of the acrylic prepolymer is 50-600 weight parts, and the content of the acrylate monomers is 30-300 weight parts;
the functional factor is an organic modified inorganic metal oxide.
2. The composition of claim 1, wherein the inorganic metal oxide is selected from TiO2、CuO、ZnO2And ZrO2One or more of;
preferably, the functional factor is prepared by a method comprising the following steps:
(1) first contacting an inorganic metal oxide with a coupling agent;
(2) and (2) carrying out second contact on the material obtained in the step (1) and carboxylic acid compounds.
3. The composition according to claim 1, wherein the particle size of the functional factor is 1-5 μm, preferably 1-3 μm.
4. The composition of claim 1, wherein the acrylic prepolymer is a multifunctional matrix resin;
preferably, the multifunctional base resin is a photocurable resin;
more preferably, the multifunctional base resin is an acrylic resin; the acrylic resin is selected from any one or more of epoxy acrylic resin, polyester acrylic resin and polyether acrylic resin;
preferably, the acrylate monomer is an acrylate monomer or a methacrylate monomer with functionality ≧ 2.
5. The composition of any one of claims 1-4, wherein the composition further comprises an adjuvant;
preferably, the auxiliary agent comprises a photoinitiator and a leveling agent;
preferably, the photoinitiator is contained in an amount of 20 to 150 parts by weight and the leveling agent is contained in an amount of 20 to 150 parts by weight, relative to 100 parts by weight of the AG modified particles.
6. The composition of any one of claims 1-4, wherein the composition further comprises an organic solvent; the organic solvent is selected from any one or more of alcohols, ketones, alkanes, esters and ethers;
preferably, the organic solvent is selected from any one or more of butanone, propylene glycol methyl ether, 4-methyl-2-pentanone, propylene glycol methyl ether acetate, ethyl acetate and butyl acetate.
7. An antibacterial AG coating liquid characterized by containing the composition as set forth in any one of claims 1 to 6 or prepared from the composition.
8. The antibacterial AG writing film is characterized by comprising a base material layer and an antibacterial AG coating coated on the surface of the base material layer; the antibacterial AG coating layer is prepared from the antibacterial AG coating liquid of claim 7, or the composition of any one of claims 1 to 6.
9. The anti-microbial AG writing film according to claim 8, further comprising a pre-treatment layer disposed between the substrate layer and the anti-microbial AG coating layer; the pretreatment layer is selected from any one or more of polyester, polyurethane and acrylic;
preferably, the thickness of the pretreatment layer is 0.01-1 μm;
preferably, the antibacterial AG coating layer has a thickness of 1 μm to 6 μm, more preferably 3 μm to 5 μm.
10. A method for producing the antibacterial AG writing film according to claim 8 or 9, characterized by comprising performing the following steps using the antibacterial AG coating liquid composition according to any one of claims 1 to 6 as a raw material:
(i) mixing the antibacterial AG coating liquid composition to obtain an antibacterial AG coating liquid;
(ii) coating the antibacterial AG coating liquid obtained in the step (1) on a substrate layer;
(iii) and (3) drying the substrate layer treated in the step (2) and curing the AG coating liquid.
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