CN115369684A - Hardening layer coating liquid and antibacterial paper film - Google Patents
Hardening layer coating liquid and antibacterial paper film Download PDFInfo
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- CN115369684A CN115369684A CN202110548798.3A CN202110548798A CN115369684A CN 115369684 A CN115369684 A CN 115369684A CN 202110548798 A CN202110548798 A CN 202110548798A CN 115369684 A CN115369684 A CN 115369684A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 64
- 238000000576 coating method Methods 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims abstract description 54
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 239000002245 particle Substances 0.000 claims abstract description 55
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 47
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 37
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 21
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- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims description 21
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 3
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims 5
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- 238000002360 preparation method Methods 0.000 description 9
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- 239000006185 dispersion Substances 0.000 description 8
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 4
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- 150000002460 imidazoles Chemical class 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical compound COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 2
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- 239000004332 silver Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 229940044120 2-n-octyl-4-isothiazolin-3-one Drugs 0.000 description 1
- UYWWLYCGNNCLKE-UHFFFAOYSA-N 2-pyridin-4-yl-1h-benzimidazole Chemical group N=1C2=CC=CC=C2NC=1C1=CC=NC=C1 UYWWLYCGNNCLKE-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- PORQOHRXAJJKGK-UHFFFAOYSA-N 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone Chemical compound CCCCCCCCN1SC(Cl)=C(Cl)C1=O PORQOHRXAJJKGK-UHFFFAOYSA-N 0.000 description 1
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 208000037157 Azotemia Diseases 0.000 description 1
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- 241000588724 Escherichia coli Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 206010040047 Sepsis Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- NTQGILPNLZZOJH-UHFFFAOYSA-N disilicon Chemical compound [Si]#[Si] NTQGILPNLZZOJH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of functional films, and particularly relates to a hardening layer coating liquid and a paper-like film. The invention provides a hardening layer coating liquid and a paper-like film, aiming at solving the problem that the existing paper-like film cannot give consideration to both antibacterial performance and paper-like feeling. The hardened layer coating liquid contains a hexafunctional group polyurethane acrylic resin oligomer, a tetrafunctional group polyurethane acrylic resin oligomer, an acrylate monomer, silicon dioxide particles, an auxiliary agent, an organic antibacterial agent, a photoinitiator and propylene glycol methyl ether; the silica particles comprise silica inorganic macro particles, silica inorganic middle particles and silica inorganic small particles, the particle size of the silica inorganic macro particles is 10-15 mu m, the particle size of the silica inorganic middle particles is 3-4 mu m, and the particle size of the silica inorganic small particles is 0.3-0.6 mu m; the percentage is weight percentage. The hardened layer coating liquid forms a hardened layer of the paper-like film after being cured, and has good paper-like feel and antibacterial performance.
Description
Technical Field
The invention belongs to the technical field of functional films, and particularly relates to a hardening layer coating liquid and an antibacterial paper film.
Background
The paper-like film can be changed into paper, is used for designing drawing and writing, and has the advantages of paper texture, no continuous touch, no slip and the like. Paper-like films are widely applied to screens of mobile phones, tablet computers and electronic blackboards, market demand is increased year by year, and the paper-like films are accepted by professional people, have no replaceable product experience in writing and drawing, if fingers directly contact the film surface of the paper-like films, if a large amount of bacteria are generated on the film surface, the health of human bodies can be indirectly harmed, for example, escherichia coli can cause gastrointestinal tract infection or urinary tract infection and other local tissue organ infections of people and various animals under certain conditions, and diarrhea is caused. Staphylococcus aureus is a common food-borne pathogenic bacterium and widely exists in natural environment. Under proper conditions, staphylococcus aureus can produce enterotoxin to cause skin suppurative infection, even septicemia, uremia and other serious diseases. The existing paper-like film in the market has the defects of poor wear-resisting effect, poor damping feeling, poor antibacterial effect or no antibacterial effect.
Chinese patent publication No. CN 210481274U (published as 2019, 08 and 23) discloses a paper-like film, which comprises a PET frosted base film coated with a silver ion antibacterial agent, and although the antibacterial effect is a certain degree, the antibacterial effect is only a thin layer on the film surface, and the antibacterial effect lasts for a short time.
Disclosure of Invention
In order to solve the problem of poor damping feeling of the conventional paper-like film, the invention provides a hardened layer coating liquid and an antibacterial paper-like film, wherein the hardened layer coating liquid is cured to form a hardened layer of the antibacterial paper-like film, so that the antibacterial paper-like film has good damping feeling.
Further, in order to solve the problem that the duration time of the antibacterial effect of the existing paper-like film is short, the invention provides the hardening layer coating liquid and the antibacterial paper-like film.
The invention provides a hardened layer coating liquid, which comprises a high-functional agglomerated urethane acrylic resin oligomer, an acrylate monomer, an auxiliary agent, an antibacterial agent and silicon dioxide particles; the silica particles comprise 0.6-0.8% of silica inorganic macroparticles, 1-2.5% of silica inorganic mesoparticles and 2-3% of silica inorganic macroparticles, the particle size of the silica inorganic macroparticles is 10-15 mu m, the particle size of the silica inorganic mesoparticles is 3-4 mu m, and the particle size of the silica inorganic mesoparticles is 0.3-0.6 mu m; the percentage is weight percentage.
Further, the high-functional group polyurethane acrylic resin oligomer comprises a hexafunctional group polyurethane acrylic resin oligomer and a tetrafunctional group polyurethane acrylic resin oligomer.
Further, the hardened layer coating liquid comprises 10-30% of hexa-functional group polyurethane acrylic resin oligomer, 15-25% of tetrafunctional group polyurethane acrylic resin oligomer, 10-18% of acrylate monomer, 0.6-0.8% of silica inorganic macro-particles, 1-2.5% of silica inorganic medium particles, 2-3% of silica inorganic small particles, 0.2-0.3% of auxiliary agent, 1-4.5% of antibacterial agent, 1-2% of photoinitiator and 28.2-53.2% of propylene glycol methyl ether. The percentage is weight percentage.
Further, the auxiliary agent is a leveling agent.
Further, the solid content of the hardened layer coating liquid is 22-56%, and the percentage is weight percentage.
Further, the hardened layer coating liquid comprises 25-30% of hexa-functional group polyurethane acrylic resin oligomer, 15-20% of tetrafunctional group polyurethane acrylic resin oligomer, 10-18% of acrylate monomer, 0.8% of silica inorganic large particle, 1.5-2.5% of silica inorganic medium particle, 2.5-3% of silica inorganic small particle, 0.2-0.3% of auxiliary agent, 2.5-4.5% of antibacterial agent, 1.3-2% of photoinitiator and 28.2-36.1% of propylene glycol methyl ether. The foregoing technical solutions include example 3 and examples 5-6.
Further, the solid content of the hardened layer coating liquid is 35-56%, and the percentage is weight percentage.
Further, the leveling agent is a siloxane leveling agent.
The invention further provides an antibacterial paper film which comprises a substrate and a hardened layer, wherein the hardened layer is attached to the surface of the substrate, and the hardened layer is formed after the hardened layer coating liquid is solidified.
Further, a bottom coating is arranged on the base material, and a hardening layer is coated on the bottom coating.
Further, the thickness of the base material is 100-188 μm, and the thickness of the hardened layer is 8-15 μm; the substrate is a PET substrate.
Further, the antibacterial agent is selected from one of an isothiazolone derivative or an imidazole derivative or a mixture of two of the isothiazolone derivative and the isothiazolone derivative, wherein the isothiazolone derivative is selected from one of 1, 2-benzisothiazolin-3-one (BIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-octyl-3 (2H) -isothiazolone, 2-octyl-3 (2H) -isothiazolone or diuron or a combination of at least two of the isothiazolone derivative and the imidazole derivative; the imidazole derivative is selected from 2-benzimidazole methyl carbamate (BCM).
Principle of
On one hand, in order to enable the film surface of the antibacterial paper film to have a paper-like feeling (namely, to improve the damping feeling of the paper-like film), a small amount of silica inorganic large particles with the particle size of 10-15 microns are added into resin, so that the film surface has a good damping feeling, and due to the fact that the addition amount of the particles is small, the particle size is too large, and particle gaps are too large, light penetrates through the paper-like film after a display screen is lightened to generate a refraction phenomenon, the flash point phenomenon is serious, and eyes are easily dazzled. Therefore, silica inorganic small particles with the particle size of 0.3-0.6 mu m and silica inorganic medium particles with the particle size of 3-4 mu m are added to fill gaps among the large particles, so that the refraction phenomenon generated by light penetrating through a paper-like film is greatly reduced, the flash point performance is improved, and certain wear resistance and hardness performance can be improved.
On the other hand, the invention solves the problem that the duration of the antibacterial effect of the antibacterial paper film is short, and the addition method of the antibacterial agent is innovative, so that the hardened layer of the whole paper-like film has antibacterial property, and is superior to the existing paper-like film only with the antibacterial surface.
Two organic antibacterial agents are added into the coating liquid, so that the film surface has good antibacterial effect.
Further, the antimicrobial agent comprises Shanghai Bitt Co
T40 and Nanjing Nandun Tianshi blue shield LD50.
Further, the antimicrobial agent is manufactured by Shanghai Bitt Co
T40 and Nanjing Nandongshi blue shield LD50, wherein the mass ratio of the T40 to the Nanjing Nandongshi blue shield LD50 is 1: 1.
Further, the present invention provides a method for preparing a hardened layer coating liquid, comprising the steps of:
(1) Weighing part of silica inorganic small particles (also called nano silica particles), inorganic electrolytic dispersant and propylene glycol methyl ether, and preparing the silica dispersion liquid by using an ultrasonic auxiliary equipment dispersion mode. The inorganic electrolyte dispersant is ammonium chloride. The small inorganic silica particles may be used to adsorb and disperse antimicrobial agents. The portion of the small inorganic silica particles may be half the amount of the small inorganic silica particles added in the entire formulation.
(2) Two antibacterial agents, shanghai Bitt Corp
Adding T40 and Nanjing Nandun Tianshi blue shield LD50 into the silicon dioxide dispersion liquid in a ratio of 1: 1, and continuously dispersing by using ultrasonic auxiliary equipment to ensure that the antibacterial agent can be well adsorbed on the surface of the inorganic small particles of the silicon dioxide to prepare the antibacterial agent dispersion liquid with 50 percent of effective components. The aforementioned 50% is the weight percentage of the antibacterial agent in the dispersion.
(3) Mixing polyurethane acrylic resin oligomer, acrylate monomer, large silicon dioxide particles, medium silicon dioxide particles, the rest small silicon dioxide particles in the step (1), an auxiliary agent, a photoinitiator, propylene glycol monomethyl ether and an antibacterial agent dispersion liquid according to a certain proportion, uniformly stirring at a high speed, and preparing a hardened layer coating liquid.
The preparation method provided by the invention can obtain excellent antibacterial performance under the condition of small using amount of the antibacterial agent. The preparation method provided by the invention reduces the production cost. In addition, the silicon dioxide small particles are not easy to sink and can be uniformly distributed in the hardened layer, so that the antibacterial agent is uniformly distributed in the hardened layer, and the problem that the duration time of the antibacterial effect of the paper-like film is short is solved.
Innovation point
1. Mixing inorganic large particles, medium particles and small particles: the damping feeling of the film surface can be increased, and the wear resistance of the film surface can be improved.
2. The preparation method of the antibacterial agent dispersion liquid comprises the following steps: and preparing a silicon dioxide dispersion liquid by using a dispersion mode of ultrasonic auxiliary equipment for part of the silicon dioxide inorganic small particles, the inorganic electrolytic dispersant and propylene glycol methyl ether, adding the two antibacterial agents into the silicon dioxide dispersion liquid, and continuously dispersing by using the ultrasonic auxiliary equipment to ensure that the antibacterial agent is well adsorbed on the surface of the silicon dioxide inorganic small particles.
Compared with the prior art, the antibacterial paper film provided by the invention has good damping sense and antibacterial performance.
Drawings
Fig. 1 is a schematic structural diagram of a paper-like film provided by the present invention.
Detailed Description
In order to make the structure and functional features and advantages of the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below:
as shown in fig. 1, the paper-like film provided by the invention sequentially comprises a paper-like film antibacterial hardened layer (also called a hard coating film or hard coating, or hardened layer) 1 and a substrate from top to bottom, wherein the hardened layer is attached to the surface of the substrate, and the substrate comprises a bottom coating layer 2 and a PET substrate 3.
In the raw materials of the hardened layer coating liquid provided by the embodiment of the invention, six functional groups are polymerizedThe urethane acrylic resin oligomer, the four-functional-group urethane acrylic resin oligomer and the acrylate monomer are produced by Guangzhou Shenwei company, the silicon dioxide inorganic particles are produced by Fuji silicon chemical company, the leveling agent is produced by Pico chemistry, and the propylene glycol methyl ether is produced by Hangzhou high-crystalline company; the antibacterial agent is selected from Shanghai Bitt
DF106，
DF25，
DF107、
T20、
T40, one or a combination of at least two of Tianshi blue shield LD50, tianshi blue shield GXY and Tianshi blue shield IBG of Nanjing south shield.
In the paper-like film provided by the embodiment of the invention,
1. base film material: highly transparent substrate, polyethylene terephthalate (PET)
Thickness: 80 to 250 μm, preferably 100 μm
A base film manufacturer: the Dongli PL2 base film comprises a base material layer and a base coating layer (also called a pretreatment layer), wherein the pretreatment layer is a chemical base on the surface of the base material layer, and can improve the adhesion between a hardening layer and the base material layer.
2. Process conditions for curing the hardened layer and coating thickness of the hardened layer:
temperature: at the temperature of 85 ℃ for 5min,
light curing energy: 400-600 mj/cm 2 ，
Coating thickness: 8-15 μm (within the thickness range, the damping feeling and the wear resistance can be ensured, and the antibacterial performance is good).
Before coating the hardened layer coating liquid on the surface of the substrate, the hardened layer coating liquid is prepared and stands for 30min.
The test instrument and the test method for the paper-like film provided by the embodiment of the invention are as follows:
1. light transmittance and haze test: the all-optical transmittance and haze of the paper-like film were measured according to JIS K-7150 using the Japanese electrochromic NDH-2000N.
2. And (3) wear resistance test: the Kunshanjing Jia instrument A20-339 adopts 0000# steel wool, 1000gf/cm according to JISK-5600 standard 2 And (4) loading, wiping the surface of the paper-like film back and forth, and detecting whether the film surface is scratched or not at the maximum limit times. The abrasion resistance times are more than 1500 times, and no scratch exists, so the wear resistance is called as high wear resistance.
3. And (3) testing pencil hardness: according to the JIS K-5600 standard, the Japanese Elcometer 3086 uses Mitsubishi type 1H-9H pencils, and the highest pencil type is used for marking 5 lines on the surface of the paper-like film under the load of 1kg, and detecting whether the film surface is scratched or not.
4. Testing the adhesion of the hardened layer: the surface of the hardened layer was tested for adhesion according to the JIS K-5600 standard, wherein 100/100 represents no peeling and 0/100 represents complete peeling.
5. And (3) testing the dynamic friction coefficient: TMI 3207, according to the standard of JISK-5600, a felt with the side length of 5cm is adopted, the load is 200g, the felt is pulled at a constant speed on the surface of the paper-like film, the dynamic friction coefficient is tested, and the higher the numerical value is, the better the damping feeling is.
6. And (3) antibacterial performance: according to JIS-Z28012000 (SGS third party report), the test results are judged as follows: the antibacterial rate is more than 99.9 percent, and the Pass is judged; the antibacterial rate was less than 99.9%, and "NG" (failure) was judged.
7. And (3) thickness testing: a paper-like film of 100mm X100 mm was cut out and the thickness thereof was measured with a micrometer.
Example 1
This example provides a hardening layer coating solution, which comprises 10% of hexa-functional group urethane acrylic resin oligomer, 20% of tetrafunctional group urethane acrylic resin oligomer, 10% of acrylate monomer, 0.6% of silica inorganic macro-particles, 2% of silica inorganic medium particles, and 2% of diSilicon oxide inorganic small particles, 0.2% of auxiliary agent, 1% of antibacterial agent, 1% of photoinitiator and 53.2% of propylene glycol methyl ether. The antimicrobial agent is prepared by Shanghai Bitt Co
T40 and Nanjing Nandong Tianshi blue shield LD50 according to the mass ratio of 1: 1.
The invention also provides an antibacterial paper-like film, which sequentially comprises a hard coating film (also called a paper-like film antibacterial hardened layer) and a PET substrate from top to bottom. The base material comprises a base material layer and a pretreatment layer, wherein the pretreatment layer is arranged on the surface of the base material layer and is a chemical substrate, and the adhesion between the hard coating film and the base material layer can be improved.
The preparation method of the antibacterial paper film comprises the following steps: the hardened layer coating liquid is applied to the surface of a substrate and photocured to form a hardened layer (i.e., a hard coating film).
The process conditions for curing the hardened layer are as follows:
temperature: 85 ℃, time: the time for 5min is less than the time for the next step,
light curing energy: 400-600 mj/cm 2 ，
Coating thickness (dry film thickness) of hardened layer: 15 μm.
Before coating the hardened layer coating liquid on the surface of the substrate, the hardened layer coating liquid is prepared according to the method provided by the invention and stands for 30min.
Examples 2 to 6
The hardened layer coating liquid and the antibacterial paper-like film provided in example 1 were formulated as shown in tables 1 and 2. The preparation method of the hardened layer coating liquid is the method provided by the invention. The method of preparing the antibacterial paper film and the substrate for the antibacterial paper film were the same as in example 1.
Table 1 part of the materials and contents of the coating liquids for a hard coat provided in examples 1 to 6
TABLE 2 partial materials and contents of coating liquids for hardened layer provided in examples 1 to 6
| Serial number | Inorganic small particles | Leveling agent | Antibacterial agent | Photoinitiator | Propylene glycol methyl ether |
| Example 1 | 2％ | 0.2％ | 1％ | 1％ | 53.2％ |
| Example 2 | 2％ | 0.3％ | 2％ | 1.2％ | 40.9％ |
| Example 3 | 2.5％ | 0.3％ | 2.5％ | 1.3％ | 36.1％ |
| Example 4 | 3％ | 0.3％ | 3％ | 1.5％ | 29.5％ |
| Example 5 | 3％ | 0.2％ | 4％ | 1.3％ | 28.2％ |
| Example 6 | 3％ | 0.3％ | 4.5％ | 2％ | 28.9％ |
Comparative example 1
Comparative example 1 differs from example 6 in that: the antibacterial agent is a silver ion inorganic antibacterial agent, specifically a Shanghai Runhe silver series inorganic antibacterial agent RHA-T3 (the main component is silver ions), the silver series inorganic antibacterial agent is coated on the surface of the paper-like film, and the components and the parts by weight thereof are shown in tables 3 and 4.
The preparation method and the process parameters of the hard coating film are the same as those of example 6.
Comparative example 2
Comparative example 2 differs from comparative example 1 in that: isothiazolone derivative, imidazole derivative or a mixture of both, each component and parts by weight thereof are shown in tables 3 and 4.
The preparation method and the process parameters of the hard coating film are the same as those of example 6.
Comparative example 3
Comparative example 3 differs from comparative example 2 in that: the weight part of the antibacterial agent is 5%, and the components and the weight parts thereof are shown in tables 3 and 4.
The preparation method and the process parameters of the hard coating film are the same as those of example 6.
Comparative example 4
Comparative example 4 differs from comparative example 3 in that: the particle diameter of the silica particles in the antibacterial agent dispersion liquid was 3 to 4 μm, and the components and their parts by weight are shown in tables 3 and 4.
The preparation method and the process parameters of the hard coating film are the same as those of example 6.
Table 3 partial materials and contents of coating liquids for hard coat layer provided in comparative examples 1 to 4
TABLE 4 partial raw materials and contents of coating liquids for hard coat layer provided in comparative examples 1 to 4
TABLE 5 results of examining the properties of hardened layers formed from the hardened layer coating liquids provided in examples 1 to 6 and comparative examples 1 to 4
Table 6 results of examining properties of hardened layers formed from the hardened layer coating liquids provided in examples 1 to 6 and comparative examples 1 to 4
| Serial number | Adhesive force% | Coefficient of dynamic friction | Antibacterial property | Antibacterial property (after abrasion resistance test) |
| Example 1 | 100 | 0.32 | PASS | PASS |
| Example 2 | 100 | 0.33 | PASS | PASS |
| Example 3 | 100 | 0.38 | PASS | PASS |
| Example 4 | 100 | 0.37 | PASS | PASS |
| Example 5 | 100 | 0.39 | PASS | PASS |
| Example 6 | 100 | 0.38 | PASS | PASS |
| Comparative example 1 | 100 | 0.37 | PASS | NG |
| Comparative example 2 | 100 | 0.39 | NG | NG |
| Comparative example 3 | 100 | 0.38 | PASS | PASS |
| Comparative example 4 | 100 | 0.39 | PASS | NG |
The above experimental data show that the hard coating films in the embodiments 1 to 6 of the present invention have good comprehensive properties, good damping feeling, wear resistance and antibacterial properties, and especially after the wear resistance test, the antibacterial properties are also good. The selection of the antibacterial agent, the addition amount of the antibacterial agent and the addition mode of the antibacterial agent can directly influence the antibacterial performance of the hard coating film, and when the antibacterial agent in the comparative example 1 is replaced by a silver-based inorganic antibacterial agent and coated on the surface of the paper-like film, the antibacterial performance is NG after an abrasion resistance test. In comparative example 2, when the added amount of the antibacterial agent was less than 0.5%, the paper-like film antibacterial performance was NG. In comparative example 4, after the antibacterial agent dispersion liquid in which the small particles were replaced with the medium particles was subjected to the abrasion resistance test, the antibacterial performance was NG (failed).
The examples 3, 5 and 6 have better comprehensive performance, and the hardened layer of the antibacterial paper film has more excellent wear resistance and antibacterial performance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. All equivalent changes and modifications made according to the disclosure of the present invention are covered by the scope of the claims of the present invention.
Claims (10)
1. A hardened layer coating liquid, which is characterized in that the hardened layer coating liquid comprises a high-functional agglomerated urethane acrylic resin oligomer, an acrylate monomer, an auxiliary agent, an antibacterial agent and silicon dioxide particles; the silica particles comprise 0.6-0.8% of silica inorganic macroparticles, 1-2.5% of silica inorganic mesoparticles and 2-3% of silica inorganic macroparticles, the particle size of the silica inorganic macroparticles is 10-15 mu m, the particle size of the silica inorganic mesoparticles is 3-4 mu m, and the particle size of the silica inorganic mesoparticles is 0.3-0.6 mu m; the percentage is weight percentage.
2. The hard layer coating liquid as defined in claim 1, wherein the high-functional group urethane acrylate resin oligomer includes a hexafunctional group urethane acrylate resin oligomer and a tetrafunctional group urethane acrylate resin oligomer.
3. The hardened layer coating liquid of claim 2, wherein the hardened layer coating liquid comprises 10 to 30% of a hexafunctional urethane acrylate oligomer, 15 to 25% of a tetrafunctional urethane acrylate oligomer, 10 to 18% of an acrylate monomer, 0.6 to 0.8% of silica inorganic macro-particles, 1 to 2.5% of silica inorganic medium particles, 2 to 3% of silica inorganic small particles, 0.2 to 0.3% of an auxiliary agent, 1 to 4.5% of an antibacterial agent, 1 to 2% of a photoinitiator, and 28.2 to 53.2% of propylene glycol methyl ether.
4. The hardened layer coating liquid as claimed in claim 3, wherein the auxiliary agent is a leveling agent.
5. The hardened layer coating liquid as claimed in claim 3, wherein said hardened layer coating liquid comprises 25 to 30% of a hexafunctional urethane acrylic resin oligomer, 15 to 20% of a tetrafunctional urethane acrylic resin oligomer, 10 to 18% of an acrylate monomer, 0.8% of silica inorganic macroparticles, 1.5 to 2.5% of silica inorganic mesoparticles and 2.5 to 3% of silica inorganic mesoparticles, 0.2 to 0.3% of an auxiliary agent, 2.5 to 4.5% of an antibacterial agent, 1.3 to 2% of a photoinitiator, and 28.2 to 36.1% of propylene glycol methyl ether.
6. The hardened layer coating liquid as claimed in claim 5, wherein the hardened layer coating liquid has a solid content of 35 to 56% by weight.
7. The hardened layer coating liquid as claimed in claim 6, wherein the leveling agent is a siloxane leveling agent.
8. An antibacterial paper film comprising a substrate and a hardened layer, wherein the hardened layer is attached to the surface of the substrate, and the hardened layer is formed by curing the hardened layer coating liquid according to any one of claims 1 to 7.
9. The antibacterial paper film according to claim 8, wherein a primer layer is provided on the substrate, and a hardened layer is coated on the primer layer.
10. The antibacterial paper film according to claim 7, wherein the substrate has a thickness of 100 to 188 μm, and the hardened layer has a thickness of 8 to 15 μm; the substrate is a PET substrate.
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| CN212540765U (en) * | 2020-06-18 | 2021-02-12 | 深圳市蓝禾技术有限公司 | Anti-falling paper film and electronic equipment |
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