CN115369684B - Hardened layer coating liquid and antibacterial paper film - Google Patents
Hardened layer coating liquid and antibacterial paper film Download PDFInfo
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- CN115369684B CN115369684B CN202110548798.3A CN202110548798A CN115369684B CN 115369684 B CN115369684 B CN 115369684B CN 202110548798 A CN202110548798 A CN 202110548798A CN 115369684 B CN115369684 B CN 115369684B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 52
- 239000007788 liquid Substances 0.000 title claims abstract description 51
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000002245 particle Substances 0.000 claims abstract description 49
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 42
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 41
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 12
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 claims abstract description 12
- 239000004814 polyurethane Substances 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- -1 acrylic ester Chemical class 0.000 abstract description 8
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 70
- 230000000052 comparative effect Effects 0.000 description 22
- 238000013016 damping Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000005299 abrasion Methods 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000004599 antimicrobial Substances 0.000 description 4
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver 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
- 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
- 238000001723 curing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 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
- 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
- 239000005510 Diuron Substances 0.000 description 1
- 101710146739 Enterotoxin Proteins 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
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N carbendazim Chemical group C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000147 enterotoxin Substances 0.000 description 1
- 231100000655 enterotoxin Toxicity 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 208000013223 septicemia Diseases 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 208000009852 uremia Diseases 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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 application belongs to the technical field of functional films, and particularly relates to a hardening layer coating liquid and a paper-like film. The application provides a hardening layer coating liquid and a paper-like film, which aim to solve the problem that the existing paper-like film cannot achieve both antibacterial performance and paper-like feel. The hardening layer coating liquid comprises a hexafunctional polyurethane acrylic resin oligomer, a tetrafunctional polyurethane acrylic resin oligomer, an acrylic ester monomer, silica particles, an auxiliary agent, an organic antibacterial agent, a photoinitiator and propylene glycol methyl ether; the silica particles comprise silica inorganic large particles, silica inorganic medium particles and silica inorganic small particles, wherein the particle size of the silica inorganic large particles is 10-15 mu m, the particle size of the silica inorganic medium 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 content is weight percentage content. The hardening layer coating liquid forms a hardening layer of the paper-like film after solidification, and has good paper-like feel and antibacterial property.
Description
Technical Field
The application 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 film is also called a writing film, can be used as a screen, is used for designing drawing and writing, and has the advantages of paper texture, continuous touch, no slipping and the like. The paper-like film is widely applied to the screens of mobile phones, tablet computers and electronic blackboards, the market demand is increased year by year, and especially the paper-like film is accepted by some professionals, and has irreplaceable product experience in writing and drawing. Staphylococcus aureus is a common food-borne pathogenic bacterium and is widely found in natural environments. Staphylococcus aureus can produce enterotoxin under proper conditions, and can cause skin suppurative infection, even severe diseases such as septicemia, uremia and the like. The existing paper-like films in the market have the defects of poor wear resistance effect, poor damping effect, poor antibacterial effect or no antibacterial effect.
Chinese patent publication No. CN 210481274U (publication No. 2019, no. 08 and No. 23) discloses a paper-like film, which comprises a layer of silver ion antibacterial agent coated on a PET frosted base film, and has a certain antibacterial effect, but the antibacterial effect is continuously short in time due to the fact that the antibacterial layer is only thin on the film surface.
Disclosure of Invention
On the one hand, in order to solve the problem of poor damping feeling of the existing paper-like film, the application provides a hardening layer coating liquid and an antibacterial paper-like film, wherein the hardening layer coating liquid forms a hardening layer of the antibacterial paper-like film after solidification, so that the antibacterial paper-like film has good damping feeling.
Furthermore, in order to solve the problem that the duration of the antibacterial effect of the existing paper-like film is short, the application provides the hardening layer coating liquid and the antibacterial paper-like film, and the hardening layer coating liquid forms the hardening layer of the antibacterial paper-like film after solidification, so that the antibacterial paper-like film has good damping sense and long duration of the antibacterial effect.
The application provides a hardening layer coating liquid, which comprises high-functional polyurethane acrylic resin oligomer, acrylic ester monomer, auxiliary agent, antibacterial agent and silicon dioxide particles; the silica particles comprise 0.6-0.8% of silica inorganic macroparticles, 1-2.5% of silica inorganic median particles and 2-3% of silica inorganic small particles, wherein the particle size of the silica inorganic macroparticles is 10-15 mu m, the particle size of the silica inorganic median 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 content is weight percentage content.
Further, the high functional urethane acrylate oligomer includes a six functional urethane acrylate oligomer, and a four functional urethane acrylate oligomer.
Further, the coating liquid for the hardening layer comprises 10 to 30 percent of hexafunctional polyurethane acrylic resin oligomer, 15 to 25 percent of tetrafunctional polyurethane acrylic resin oligomer, 10 to 18 percent of acrylic ester monomer, 0.6 to 0.8 percent of silica inorganic large particles, 1 to 2.5 percent of silica inorganic medium particles, 2 to 3 percent of silica inorganic small particles, 0.2 to 0.3 percent of auxiliary agent, 1 to 4.5 percent of antibacterial agent, 1 to 2 percent of photoinitiator and 28.2 to 53.2 percent of propylene glycol methyl ether. The percentage content is weight percentage content.
Further, the auxiliary agent is a leveling agent.
Further, the solid content of the hardening layer coating liquid is 22-56%, and the percentage content is weight percentage.
Further, the coating liquid for the hardening layer comprises 25-30% of a six-functional polyurethane acrylic resin oligomer, 15-20% of a four-functional polyurethane acrylic resin oligomer, 10-18% of an acrylic ester monomer, 0.8% of silica inorganic macroparticles, 1.5-2.5% of silica inorganic medium particles, 2.5-3% of silica inorganic small particles, 0.2-0.3% of an auxiliary agent, 2.5-4.5% of an antibacterial agent, 1.3-2% of a photoinitiator and 28.2-36.1% of propylene glycol methyl ether. The foregoing technical solutions include embodiment 3 and embodiments 5-6.
Further, the solid content of the hardening layer coating liquid is 35-56%, and the percentage content is weight percentage.
Further, the leveling agent is a siloxane leveling agent.
The application also provides an antibacterial paper film, which comprises a base material and a hardening layer, wherein the hardening layer is attached to the surface of the base material, and the hardening layer is formed after the hardening layer coating liquid is solidified.
Further, the base material is provided with an undercoat layer, and a hardening layer is coated on the undercoat layer.
Further, the thickness of the base material is 100-188 μm, and the thickness of the hardening layer is 8-15 μm; the substrate is a PET substrate.
Further, the antibacterial agent is selected from one or a mixture of two of isothiazolone derivatives or imidazole derivatives, wherein the isothiazolone derivatives are selected from one or a combination of at least two 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; the imidazole derivative is selected from methyl 2-Benzimidazole Carbamate (BCM).
Principle of
On the other hand, in order to make the film surface of the antibacterial paper-like film have paper-like feel (i.e. to improve the damping feel of the paper-like film), a small amount of inorganic large silica particles with the particle size of 10-15 μm are added into the resin, so that the film surface has good damping feel, and the light rays penetrate the paper-like film to generate refraction phenomenon after the display screen is lightened due to the fact that the particle addition amount is small, the particle size is overlarge and the particle gap is overlarge, so that the flash point phenomenon is serious and eyes are easy to shake. Therefore, the inorganic small silica particles with the particle size of 0.3-0.6 mu m and the inorganic medium silica particles with the particle size of 3-4 mu m are added to fill gaps among large particles, so that the refraction phenomenon generated when light penetrates through the paper-like film is greatly reduced, the flash point performance is improved, and certain wear resistance and hardness performance are also improved.
On the other hand, the application solves the problem of short duration of the antibacterial effect of the antibacterial paper film, and the addition method of the antibacterial agent has innovation, so that the hardened layer of the whole paper-like film has antibacterial property, and is superior to the existing paper-like film with antibacterial property only on the surface.
Two organic antibacterial agents are added into the coating liquid, so that the film surface has good antibacterial effect.
Further, the antibacterial agent includes Shanghai Bitt companyT40 and Nanjing Shi blue shield LD50.
Further, the antibacterial agent is manufactured by Shanghai Bitt CoT40 and Nanjing Shi blue shield LD50, the mass ratio of the two is 1:1.
Further, the present application provides a method for preparing a hardened layer coating liquid, comprising the steps of:
(1) And weighing part of silica inorganic small particles (also called nano silica particles), inorganic electrolytic dispersant and propylene glycol methyl ether, and preparing silica dispersion liquid by using an ultrasonic auxiliary device to disperse. The inorganic electrolyte dispersant is ammonium chloride. Silica inorganic small particles can be used to adsorb and disperse the antimicrobial agent. The portion of the silica inorganic small particles may be half the amount of silica inorganic small particles added to the entire formulation.
(2) Two antibacterial agents, shanghai Bite CoT40 and Nanjing Shi blue shield LD50 are added to the silica dispersion in a 1:1 ratio, the dispersion is continued by means of the ultrasound-assisted device, the antibacterial agent can be well adsorbed on the surface of the inorganic small silica particles, and the antibacterial agent dispersion liquid with 50% of active ingredients is prepared. The 50% is the weight percentage of the antimicrobial agent in the dispersion.
(3) Mixing polyurethane acrylic resin oligomer, acrylic ester monomer, silica macroparticles remained in the step (1), auxiliary agent, photoinitiator, propylene glycol methyl ether and antimicrobial agent dispersion liquid according to a certain proportion, and uniformly stirring at a high speed to prepare the hardening layer coating liquid.
The preparation method provided by the application can ensure that excellent antibacterial performance can be obtained under the condition of small dosage of the antibacterial agent. The preparation method provided by the application reduces the production cost. And moreover, the small silica particles are not easy to sink and can be uniformly distributed in the hardening layer, so that the antibacterial agent is uniformly distributed in the hardening layer, and the problem of short duration of the antibacterial effect of the paper-like film is solved.
Innovation point
1. Inorganic macroparticles, mesoparticles, and microparticles: the damping sense of the membrane surface can be increased, and the wear resistance of the membrane surface can be improved.
2. The preparation method of the antibacterial agent dispersion liquid comprises the following steps: and adding two antibacterial agents into the silica dispersion liquid, and continuing to disperse through ultrasonic auxiliary equipment, so that the antibacterial agents are well adsorbed on the surfaces of the silica inorganic small particles.
Compared with the prior art, the antibacterial paper film provided by the application has good damping sense and antibacterial performance.
Drawings
Fig. 1 is a schematic structural diagram of a paper-like film according to the present application.
Detailed Description
For a better understanding of the present application, its construction, and the functional features and advantages attained by the same, reference should be made to the accompanying drawings in which:
as shown in fig. 1, the paper-like film provided by the application sequentially comprises a paper-like film antibacterial hardening layer (also called a hard coating film or a hard coating layer, or a hardening layer) 1 and a base material from top to bottom, wherein the hardening layer is attached to the surface of the base material, and the base material comprises a base coat layer 2 and a PET base material 3.
In the raw materials of the hardening layer coating liquid provided by the embodiment of the application, the hexafunctional polyurethane acrylic resin oligomer, the tetrafunctional polyurethane acrylic resin oligomer and the acrylic ester monomer are produced by Guangzhou Shenwei corporation, the silicon dioxide inorganic particles are produced by Fuji silicon chemical corporation, the leveling agent is produced by Pick chemistry, and the propylene glycol methyl ether is produced by Hangzhou high-crystal corporation; the antibacterial agent is selected from Shanghai Bitt companyDF106，/>DF25，/>DF107、T20、/>T40, tianshi blue shield LD50, tianshi blue shield GXY and Tianshi blue shield IBG of Nanjing south shield or a combination of at least two.
In the paper-like film provided by the embodiment of the application,
1. base film material: highly transparent substrates, polyethylene terephthalate (PET)
Thickness: 80 μm to 250 μm, preferably 100 μm
Base film manufacturer: the Dongli PL2 base film comprises a base material layer and a bottom coating layer (also called a pretreatment layer), wherein the pretreatment layer is a chemical substrate on the surface of the base material layer, so that the adhesion between the hardening layer and the base material layer can be improved.
2. Process conditions for curing the hardened layer and coating thickness of the hardened layer:
temperature: at the temperature of 85 ℃ for 5min,
photo-curing energy: 400-600 mj/cm 2 ，
Coating thickness: 8-15 mu m (within the thickness range, not only good damping sense and wear resistance can be ensured, but also good antibacterial performance can be achieved).
Before the hardening layer coating liquid is coated on the surface of the substrate, the hardening layer coating liquid is prepared and kept stand for 30min.
The test instrument and the test method for the paper-like film provided by the embodiment of the application are as follows:
1. light transmittance and haze test: the paper-like film was tested for its full light transmittance and haze according to JISK-7150 standard in Japanese electrochromic NDH-2000N.
2. Abrasion resistance test: kunshanjia instrument A20-339, according to JISK-5600 standard, uses 0000# steel wool, 1000gf/cm 2 And (3) loading, wiping the surface of the paper-like film back and forth, and detecting the maximum limit number of scratch of the film surface. The abrasion resistance times are above 1500 times, and no scratch exists, so that the abrasion resistance is high.
3. Pencil hardness test: in Elcometer 3086, the highest pencil type was measured by drawing 5 lines on the surface of a paper-like film with a load of 1kg using Mitsubishi type 1H to 9H pencils according to JISK-5600 standard.
4. Hardened layer adhesion test: the surface of the hardened layer was tested for adhesion according to JISK-5600, wherein 100/100 represents no drop and 0/100 represents complete drop.
5. Dynamic coefficient of friction test: TMI 3207 adopts felt with the side length of 5cm according to JISK-5600 standard, loads 200g, pulls at a uniform speed on the surface of the paper-like film, tests dynamic friction coefficient, and the higher the numerical value is, the better the damping sense is.
6. Antibacterial properties: determination according to JIS-Z28012000 (report from SGS third party): the antibacterial rate is more than 99.9 percent, and the Pass is judged; the antibacterial rate was less than 99.9%, and "NG" (reject) was judged.
7. Thickness test: the 100mm by 100mm paper-like film was cut and its thickness was measured with a micrometer.
Example 1
The present example provides a hardened layer coating liquid comprising 10% of a six-functional urethane acrylic oligomer, 20% of a four-functional urethane acrylic oligomer, 10% of an acrylate monomer, 0.6% of silica inorganic macroparticles, 2% of silica inorganic macroparticles, 0.2% of an auxiliary agent, 1% of an antimicrobial agent, 1% of a photoinitiator, and 53.2% of propylene glycol methyl ether. The antibacterial agent is manufactured by Shanghai Bitt CoT40 and Nanjing Shi blue shield LD50 the composition is prepared according to the mass ratio of 1:1.
The application also provides an antibacterial paper film which sequentially comprises a hard coating film (also called a paper film antibacterial hardening layer) and a PET base material from top to bottom. The substrate comprises a substrate layer and a pretreatment layer, wherein the pretreatment layer is a layer of chemical base on the surface of the substrate layer, so that the adhesion between the hard coating film and the substrate layer can be improved.
The preparation method of the antibacterial paper film comprises the following steps: the hardening layer coating liquid is coated on the surface of the substrate, and the hardening layer (i.e., the hard coating film) is formed by photo-curing.
The process conditions for curing the hardened layer are as follows:
temperature: 85 ℃ and the time is as follows: for 5min, the time period is set to be short,
photo-curing energy: 400-600 mj/cm 2 ，
Coating thickness of hardened layer (dry film thickness): 15 μm.
Before the hardening layer coating liquid is coated on the surface of the substrate, the hardening layer coating liquid is prepared according to the method provided by the application and stands for 30min.
Examples 2 to 6
The formulation of the cured layer coating liquid and the antibacterial paper film as provided in example 1 are shown in tables 1 and 2. The preparation method of the hardening layer coating liquid is the method provided by the application. The base material of the antibacterial paper film and the preparation method of the antibacterial paper film are the same as in example 1.
TABLE 1 partial raw materials and contents of the coating liquids for the hardening layer provided in examples 1 to 6
TABLE 2 partial raw materials and contents of the coating liquids for the hardening layer provided in examples 1 to 6
| Sequence 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
Compared with example 6, comparative example 1 is different in that: the antibacterial agent is silver ion inorganic antibacterial agent, specifically Shanghai Runhe silver inorganic antibacterial agent RHA-T3 (the main component is silver ion), the silver inorganic antibacterial agent is coated on the surface of the paper-like film, 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 were the same as in example 6.
Comparative example 2
Comparative example 2 is different from comparative example 1 in that: isothiazolone derivatives, imidazole derivatives 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 were the same as in example 6.
Comparative example 3
Comparative example 3 is different from comparative example 2 in that: the antibacterial agent was 5% by weight, and the components and parts by weight thereof are shown in tables 3 and 4.
The preparation method and the process parameters of the hard coating film were the same as in example 6.
Comparative example 4
Comparative example 4 is different from comparative example 3 in that: the particle diameter of the silica particles in the antibacterial agent dispersion was 3 to 4. Mu.m, and the components and parts by weight thereof are shown in tables 3 and 4.
The preparation method and the process parameters of the hard coating film were the same as in example 6.
TABLE 3 partial raw materials and contents of the coating liquids for the hardening layer provided in comparative examples 1 to 4
TABLE 4 partial raw materials and contents of the coating liquids for the hardening layer provided in comparative examples 1 to 4
TABLE 5 test results of Performance of the cured layers formed from the cured layer coating liquids provided in examples 1 to 6 and comparative examples 1 to 4
TABLE 6 test results of Performance of cured layers formed from the cured layer coating liquids provided in examples 1 to 6 and comparative examples 1 to 4
| Sequence number | Adhesion% | 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 hard coating films in examples 1 to 6 of the present application are analyzed by the experimental data of the table to have good comprehensive properties, good damping feeling, wear resistance and antibacterial properties, and particularly, after wear resistance test, the antibacterial properties are as 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, when the antibacterial agent in the comparative example 1 is replaced by a silver inorganic antibacterial agent to be coated on the surface of the paper-like film, and after the abrasion resistance test, the antibacterial performance is NG. In comparative example 2, when the addition amount of the antibacterial agent is less than 0.5%, the paper-like film antibacterial property NG. In comparative example 4, after the small particles were replaced with the medium particles in the antibacterial agent dispersion, the antibacterial performance NG (reject) was subjected to the abrasion resistance test.
Among them, examples 3, 5 and 6 are better in combination property, and the hardened layer of the antibacterial paper film is more excellent in abrasion resistance and antibacterial property.
The foregoing description is only of the preferred embodiments of the present application, and is not intended to limit the scope of the present application. All equivalent changes and modifications made in accordance with the present application are intended to be covered by the scope of the appended claims.
Claims (8)
1. The hardening layer coating liquid is characterized by comprising 10% -30% of six-functional polyurethane acrylic resin oligomer, 15% -25% of four-functional polyurethane acrylic resin oligomer, 10% -18% of acrylate monomer, 0.6% -0.8% of silica inorganic macroparticles, 1% -2.5% of silica inorganic middle particles, 2% -3% of silica inorganic macroparticles, 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 particle size of the silica inorganic large particles is 10-15 mu m, the particle size of the silica inorganic medium 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 content is weight percentage content;
the antibacterial agent is prepared from BITETROL of Shanghai Bitt company ® T40 and Nanjing Shi blue shield LD50, the mass ratio of the two is 1:1;
the antibacterial agent is prepared into antibacterial agent dispersion liquid for use; the preparation method of the antibacterial agent dispersion liquid comprises the following steps: preparing a silicon dioxide dispersion liquid by using a mode of dispersing part of silicon dioxide inorganic small particles, inorganic electrolytic dispersing agents and propylene glycol methyl ether by using ultrasonic auxiliary equipment, adding two antibacterial agents into the silicon dioxide dispersion liquid, and continuously dispersing by using the ultrasonic auxiliary equipment to ensure that the antibacterial agents are well adsorbed on the surfaces of the silicon dioxide inorganic small particles; the addition amount of the partial silicon dioxide inorganic small particles is half of that of the silicon dioxide inorganic small particles in the whole formula.
2. The hardened layer coating liquid according to claim 1, characterized in that the auxiliary agent is a leveling agent.
3. The hardening layer coating liquid according to claim 1, wherein the hardening layer coating liquid comprises 25-30% of a six-functional urethane acrylic oligomer, 15-20% of a four-functional urethane acrylic oligomer, 10-18% of an acrylate monomer, 0.8% of silica inorganic macroparticles, 1.5-2.5% of silica inorganic macroparticles and 2.5-3% of silica inorganic macroparticles, 0.2-0.3% of an auxiliary agent, 2.5-4.5% of an antibacterial agent, 1.3-2% of a photoinitiator, and 28.2-36.1% of propylene glycol methyl ether.
4. The cured layer coating liquid according to claim 3, wherein the cured layer coating liquid has a solid content of 35% -56% and the percentage content is weight percentage.
5. The hardened layer coating fluid according to claim 2, characterized in that the leveling agent is a silicone leveling agent.
6. An antibacterial paper film comprising a base material and a cured layer, wherein the cured layer is attached to the surface of the base material, and the cured layer is formed by curing the cured layer coating liquid according to any one of claims 1 to 5.
7. The antimicrobial paper film of claim 6, wherein the substrate is provided with a primer layer over which the hardened layer is applied.
8. The antibacterial paper film of claim 6, wherein the thickness of the substrate is 100-188 μm and the thickness of the hardened layer is 8-15 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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| US20040225039A1 (en) * | 2001-09-11 | 2004-11-11 | Karsten Hackbarth | UV-curing anti-fingerprinting coatings |
| CN104817951A (en) * | 2015-05-26 | 2015-08-05 | 张家港康得新光电材料有限公司 | Anti-dazzle coating and anti-dazzle hardening film |
| CN109880507A (en) * | 2018-12-21 | 2019-06-14 | 宁波激智科技股份有限公司 | The hardened layer coating fluid and a kind of cured film of a kind of high abrasion, high tenacity |
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