CN116004109B - Skin-feel coating, skin-feel film and preparation method and application thereof - Google Patents
Skin-feel coating, skin-feel film and preparation method and application thereof Download PDFInfo
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- CN116004109B CN116004109B CN202310018574.0A CN202310018574A CN116004109B CN 116004109 B CN116004109 B CN 116004109B CN 202310018574 A CN202310018574 A CN 202310018574A CN 116004109 B CN116004109 B CN 116004109B
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000004814 polyurethane Substances 0.000 claims abstract description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000377 silicon dioxide Substances 0.000 claims description 30
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- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 4
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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 description 4
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- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 0.000 description 1
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- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Paints Or Removers (AREA)
Abstract
The application discloses a skin-feel coating, a skin-feel film and a preparation method and application thereof, and belongs to the technical field of skin-feel coatings. The skin-feel coating is prepared from the raw materials of antibacterial agent grafted oligomer resin, fluorine-containing antifouling UV resin, pentaerythritol tetraacrylate, polyurethane acrylate oligomer and photoinitiator; the antibacterial agent grafted oligomer resin is obtained by the addition polymerization reaction of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate and pentaerythritol triacrylate. The antibacterial agent grafted oligomer resin is bonded to a photo-cured polyacrylate macromolecular chain in a chemical bond mode, so that the preparation of a durable antibacterial anti-skin-resistance coating which is free of migration and precipitation and insoluble in water is facilitated, and the defects of migration and precipitation of an antibacterial agent and poor moisture resistance are avoided. The corresponding skin-feel coating has lasting antibacterial and antifouling functions, and the effective rate of inhibiting and killing gram-negative escherichia coli and staphylococcus aureus reaches more than 99 percent.
Description
Technical Field
The application relates to the technical field of skin-feel coatings, in particular to a skin-feel coating, a skin-feel film, a preparation method and application thereof.
Background
Along with the continuous improvement of aesthetic demands and the increasing of health safety consciousness of people, higher demands are put forward on various decorative materials, especially decorative boards, such as various furniture boards, wall panels, glass partitions, lamp decoration materials and the like, the conventional high-brightness appearance is gradually changed into semi-matte or full-matte appearance through technological innovation and technological innovation, the skin-friendly smooth hand feeling effect is superposed, the continuous improved aesthetic demands of people are met, meanwhile, certain antibacterial and antifouling functions are also provided, and the physical health of people is better protected. In daily life, people are very easy to spray some food residues, fruit juice and stains on the surfaces of the decorative materials, stains which are not cleaned in time are easy to mildew and grow various harmful bacteria such as escherichia coli, staphylococcus and streptococcus albus, and after touching the decorative materials, the bacteria on the surfaces are very easy to infect human bodies, so that the harm is brought to the body health of people. Therefore, development of a skin-feel coating material having an antibacterial and antifouling function and a skin-feel film thereof is highly favored by consumers.
The skin-feel coating in the prior art generally has no antibacterial function, and the anti-fouling auxiliary agent is free in the skin-feel coating, so that the anti-fouling auxiliary agent slowly migrates or precipitates out of the surface of the coating along with the prolongation of aging time, and the anti-fouling function is gradually weakened.
In view of this, the present application has been made.
Disclosure of Invention
One of the purposes of the present application is to provide a skin-feel coating to solve the above technical problems.
The second object of the present application is to provide a method for preparing the skin-feel coating.
The third object of the present application is to provide a skin feel film prepared from the skin feel paint.
The fourth object of the present application is to provide a method for preparing the skin feel film.
The fifth object of the present application is to provide an application of the above skin feel film.
The application can be realized as follows:
in a first aspect, the present application provides a skin feel coating, the preparation raw materials of which comprise an antimicrobial grafted oligomer resin, a fluorine-containing anti-fouling UV resin, pentaerythritol tetraacrylate, polyurethane acrylate oligomer and a photoinitiator;
the antibacterial agent grafted oligomer resin is obtained by the addition polymerization reaction of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate and pentaerythritol triacrylate.
In an alternative embodiment, the preparation raw material further comprises at least one of spherical silica micropowder, hand feeling slip agent, dispersant and diluent.
In an alternative embodiment, the preparation raw materials comprise, by mass, 3-5 parts of an antimicrobial grafted oligomer resin, 2-3.4 parts of a fluorine-containing anti-fouling UV resin, 3-5 parts of pentaerythritol tetraacrylate, 26-30 parts of a polyurethane acrylate oligomer, 2-2.1 parts of a photoinitiator, 8-9 parts of spherical silica micropowder, 0.5-0.7 part of a hand feeling slip agent, 0.1-0.2 part of a dispersing agent and 50 parts of a diluent.
In alternative embodiments, the photoinitiator comprises at least one of JRCURE184, irgacure819, and Omnirad TPO;
and/or the fluorine-containing anti-fouling UV resin comprises at least one of UV-370, lucure8696 and HY-R7935;
and/or the urethane acrylate oligomer comprises at least one of CN9002, 6196-100 and Agisyn 2423;
and/or the spherical silica micropowder comprises HM051HM and ML-SiO 2 -at least one of H20;
and/or the hand feeling slip agent comprises at least one of SY-905 and XH-A51;
and/or the dispersant comprises BYK361N.
In a second aspect, the present application provides a method of preparing a skin feel coating according to any one of the preceding embodiments, comprising the steps of: mixing the raw materials according to the proportion.
In an alternative embodiment, the raw materials are initially stirred, left to stand until the spherical silica micropowder is sufficiently wetted, then mixed for 20-25min under the condition that the shearing dispersion rotating speed is 2250-2350rpm, and left to stand for defoaming.
In an alternative embodiment, the antimicrobial grafted oligomer resin is obtained by: and (3) carrying out reflux stirring reaction on polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, a solvent and a catalyst together, then adding pentaerythritol triacrylate, and continuing the reflux stirring reaction.
In an alternative embodiment, the molar ratio of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, and pentaerythritol triacrylate is 1:2.05-2.1:1-1.05.
In an alternative embodiment, the solvent is ethyl acetate.
In an alternative embodiment, the mass of the solvent is 50% of the total mass of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, and pentaerythritol triacrylate.
In an alternative embodiment, the catalyst is dibutyltin dilaurate.
In an alternative embodiment, the mass of the catalyst is 0.01 to 0.012% of the total mass of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, and pentaerythritol triacrylate.
In an alternative embodiment, the reflux stirring reaction prior to the addition of pentaerythritol triacrylate is carried out at 70-80℃for 3-3.5 hours.
In an alternative embodiment, the reflux agitation time after addition of pentaerythritol triacrylate is 4 to 4.5 hours.
In an alternative embodiment, after the entire reflux stirring reaction is completed, the solvent is added to dilute the antimicrobial graft oligomer resin to a solids content of 50 wt.%.
In a third aspect, the present application provides a skin feel film prepared from the skin feel coating of any one of the preceding embodiments.
In a fourth aspect, the present application provides a method for preparing a skin feel film according to the previous embodiments, comprising the steps of: and (3) coating the skin-feel coating on the surface of the PET film, drying, curing by UV light irradiation, and rolling.
In an alternative embodiment, the solids content of the skin feel coating used to coat the surface of the PET film is 25wt%.
In an alternative embodiment, the oven temperatures used for drying are as follows: the first region is 42-48deg.C, the second region is 72-78deg.C, the third region is 87-93deg.C, the fourth region is 97-103 deg.C, the fifth region is 87-93 deg.C, and the sixth region is 77-83 deg.C.
In an alternative embodiment, the UV light energy is 400-500mj/cm during the preparation of the skin feel film 2 。
In an alternative embodiment, the coating speed is 15m/min during the skin feel film preparation process.
In a fifth aspect, the present application provides the use of a skin feel film as in the previous embodiments, for example as a surface mount film for a household decorative sheet.
The beneficial effects of the application include:
the skin-feel coating provided by the application has good antibacterial and antifouling effects, can be used for preparing a durable antibacterial and antifouling skin-feel coating which is free of migration and precipitation and insoluble in water, and avoids the defects of migration and precipitation of an antibacterial agent and poor moisture resistance. The corresponding skin-feel coating has lasting antibacterial and antifouling functions, has an effective rate of over 99 percent on inhibiting and killing gram-negative escherichia coli and staphylococcus aureus, and is easy to wipe clean stains.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The skin-feel paint and the skin-feel film provided by the application and the preparation method and application thereof are specifically described below.
The application provides a skin-feel coating, which is prepared from the following raw materials of antibacterial agent grafted oligomer resin, fluorine-containing antifouling UV resin, pentaerythritol tetraacrylate, polyurethane acrylate oligomer and photoinitiator.
The antibacterial agent grafted oligomer resin is obtained by the addition polymerization reaction of polyhexamethylene guanidine hydrochloride (PHMG) and Hexamethylene Diisocyanate (HDI) and pentaerythritol triacrylate (PETA). The antibacterial agent grafted oligomer resin is specifically polyhexamethylene guanidine hydrochloride grafted pentaerythritol triacrylate oligomer resin (PHMG-HDI-PETA).
Further, the preparation raw materials further comprise at least one of spherical silica micropowder, a hand feeling slip agent, a dispersing agent and a diluting agent.
Preferably, the raw materials for preparing the skin-feel coating simultaneously contain antibacterial agent grafted oligomer resin, fluorine-containing antifouling UV resin, pentaerythritol tetraacrylate, polyurethane acrylate oligomer, photoinitiator, spherical silica micropowder, hand feeling slip agent, dispersing agent and diluent.
For reference, the preparation raw materials may include 3 to 5 parts of an antibacterial agent graft oligomer resin, 2 to 3.4 parts of a fluorine-containing anti-fouling UV resin, 3 to 5 parts of pentaerythritol tetraacrylate, 26 to 30 parts of a urethane acrylate oligomer, 2 to 2.1 parts of a photoinitiator, 8 to 9 parts of spherical silica micropowder, 0.5 to 0.7 part of a hand feeling slip agent, 0.1 to 0.2 part of a dispersing agent and 50 parts of a diluent, in terms of mass fraction.
The amount of the antibacterial agent graft oligomer resin may be 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts or 5 parts, etc., or any other value within the range of 3 to 5 parts.
The amount of the fluorine-containing anti-fouling UV resin may be 2 parts, 2.2 parts, 2.5 parts, 2.8 parts, 3 parts, 3.2 parts or 3.4 parts, etc., or may be any other value within the range of 2 to 3.4 parts.
The pentaerythritol tetraacrylate may be used in an amount of 3 parts, 3.2 parts, 3.5 parts, 3.8 parts, 4 parts, 4.2 parts, 4.5 parts, 4.8 parts or 5 parts, etc., or any other value within the range of 3 to 5 parts.
The urethane acrylate oligomer may be used in an amount of 26 parts, 26.5 parts, 27 parts, 27.5 parts, 28 parts, 28.5 parts, 29 parts, 29.5 parts or 30 parts, etc., or may be used in any other amount within the range of 26 to 30 parts.
The photoinitiator may be used in an amount of 2 parts, 2.05 parts, 2.1 parts, etc., or any other value within the range of 2 to 2.1 parts.
The amount of the spherical silica fine powder may be 8 parts, 8.2 parts, 8.5 parts, 8.8 parts, 9 parts or the like, or any other value within the range of 8 to 9 parts.
The amount of the hand feeling slip agent may be 0.5 part, 0.55 part, 0.6 part, 0.65 part, 0.7 part, etc., or any other value within the range of 0.5 to 0.7 part.
The amount of the dispersant may be 0.1 part, 0.12 part, 0.15 part, 0.18 part, 0.2 part, or the like, or may be any other value within the range of 0.1 to 0.2 part.
For reference, the photoinitiator used in the present application may illustratively include at least one of JRCURE184, irgacure819, and Omnirad TPO. Among them, JRCURE184 is available from the new material stock company of the senior, the Irgacure819 is available from the basf property chemical company, and Omnirad TPO is available from the basf property chemical company.
The fluorine-containing anti-fouling UV resin may illustratively include at least one of UV-370, lucure8696, and HY-R7935. Wherein UV-370 is available from Shenzhen fluorine technology Co., ltd, lucure8696 is available from Guangzhou Ruo chemical materials Co., ltd, and HY-R7935 is available from Shanghai Hui New materials Co., ltd.
The urethane acrylate oligomer may illustratively include at least one of CN9002, 6196-100 and Agisyn 2423. Among them, CN9002 is available from sartomer (guangzhou) chemical company, 6196-100 is available from chang materials industry, inc, agisyn2423 is available from kesiji polymer (china) company.
The spherical silica micropowder may illustratively include HM051HM and ML-SiO 2 -at least one of H20. Wherein HM051HM is available from Jiangsu Hui powder technology Co., ltd 2 H20 is available from Zhejiang Mannich nanotechnology Co.
The hand slip agent may illustratively include at least one of SY-905 and XH-A51. Among them, SY-905 can be purchased from Jiangxi Sanyue New Material Co., ltd, and XH-A51 can be purchased from Guangdong Dongguan Xurihua chemical Co., ltd.
The dispersant may illustratively include BYK361N. BYK361N is available from Pick auxiliary Shanghai Co.
On the other hand, the antibacterial agent grafted oligomer resin and the fluorine-containing antifouling UV resin contained in the skin-feel coating provided by the application can endow the skin-feel coating with excellent antibacterial and antifouling functions, and the spherical silica micro powder and the hand feeling slip agent contained in the skin-feel coating can endow the skin-feel coating film with excellent matte effect and skin-friendly and slip hand feeling.
Specifically, the skin-feel coating is a UV light-curable skin-feel coating, free radical random polymerization is realized through UV light irradiation curing, and the wear-resistant skin-feel coating with antibacterial and antifouling functions can be prepared. The coating has good antibacterial property, has a valid period of not less than 5 years, and has remarkable killing effect on various bacteria and viruses such as escherichia coli and staphylococcus aureus. The reason for this is that: the polyhexamethylene guanidine hydrochloride contained in the skin-feel coating is a broad-spectrum efficient organic antibacterial agent, and has a rapid sterilization effect, and is safe and nontoxic to human bodies. The antibacterial action mechanism is mainly that polyhexamethylene guanidine hydrochloride changes the permeability of bacterial cell membranes by dissolving bacterial lipid, so that the metabolism in a bacterial body is blocked, and the aim of killing bacteria is fulfilled.
The application creatively adopts a chemical bonding technical route, and prepares the polyhexamethylene guanidine hydrochloride grafted pentaerythritol triacrylate oligomer resin (PHMG-HDI-PETA) through the addition polymerization reaction of HDI and pentaerythritol triacrylate. And then PHMG-HDI-PETA is used as an antibacterial agent capable of being cured by UV light to carry out chemical bonding modification on UV light-curing resin, the oligomer containing the guanidine group is bonded to a photo-curing polyacrylate macromolecular chain (mainly provided by pentaerythritol tetraacrylate and polyurethane acrylate oligomer) in a chemical bond mode, and the durable antibacterial coating which is free of migration precipitation and insoluble in water is prepared, so that the defects of migration precipitation and poor moisture resistance of the antibacterial agent are avoided. Compared with the conventional antibacterial agent blending method, the prepared skin-feel coating has lasting antibacterial function, has the effective rate of inhibiting and killing gram-negative escherichia coli and staphylococcus aureus up to more than 99 percent, effectively inhibits the breeding and reproduction of various bacteria on the surface of the skin-feel coating, and better protects the health of people.
The fluorine-containing UV curable resin is adopted, the UV light irradiation participates in the photo-curing reaction, and the fluorine-containing UV curable resin is grafted onto a polyacrylate macromolecular main chain (mainly provided by pentaerythritol tetraacrylate and polyurethane acrylate oligomer), so that the durable anti-fouling coating without migration precipitation is prepared, and the anti-fouling effect is obvious. Whether the oil marker is used for graffiti or common ink, fruit juice and greasy dirt stains, the ink can be wiped clean by an eraser, a wet rag, a cleaning agent, alcohol and the like. The reason for this is that: the fluorine-containing UV curable resin used in the application is an extremely low surface energy material, has low affinity with common greasy dirt stains, and is not easy to adhere to the surface of the skin-feel coating, so that the fluorine-containing UV curable resin is easy to wipe clean.
According to the application, the spherical silica micropowder and the hand feeling slip agent are adopted, on one hand, the spherical silica micropowder has a light controllable matte effect compared with the conventional irregular-morphology matting powder, and the matte effect and glossiness of the skin-feel coating are adjusted by controlling the adding proportion. Meanwhile, the spherical silica micro powder has smooth surface morphology, and particles are orderly arranged and solidified on the surface of the coating, so that the surface of the coating shows good skin-friendly and smooth hand feeling effect. On the other hand, the micro-quantity of hand feeling slip agent migrates to the surface of the coating before photo-curing because the density is smaller than that of the UV curing resin, the surface smoothness of the photo-curing resin and the spherical silica micro powder is further increased after photo-curing, and the skin feeling coating shows good slip hand feeling effect. The skin feel coating provided by the application has a pleasant matte effect and a smooth feel effect, and meets the aesthetic requirements of people on high-quality decorative materials.
For reference, the above skin feel coating has at least the following performance effects:
(1) the effective period of the antibacterial agent is more than or equal to 5 years, the inhibition rate of the antibacterial agent to gram-negative escherichia coli is more than or equal to 99 percent after the antibacterial agent is contacted for 24 hours by adopting a film-sticking method, and the inhibition rate of the antibacterial agent to gram-positive staphylococcus aureus is more than or equal to 99 percent.
(2) The black marker with model number 6881 of the available group of limited company is marked on the surface of the coating, and is easy to wipe clean by an eraser after being dried for 10 minutes at normal temperature.
(3) The hardness level of the surface pencil is not lower than HB level under 500 g load, the number of times of friction of 0000# steel wool is not less than 200 times under 1000 g load, the surface glossiness of 60 degrees is not more than 15GU, the surface friction coefficient is not more than 0.30, and the hand feeling is smooth and friendly.
Correspondingly, the application provides a preparation method of the skin-feel paint, which comprises the following steps: mixing the raw materials according to the proportion.
In some embodiments, the raw materials may be initially stirred, allowed to stand until the spherical silica micropowder is sufficiently wetted, then mixed for 20-25 minutes at a shear dispersion speed of 2250-2350rpm, allowed to stand for defoaming.
Specifically, all raw materials are added into a proper light-resistant container, dispersed and stirred for 5min by a glass rod for primary treatment, the mixture is kept stand for 20min to fully wet spherical silica micro powder, then sheared and dispersed by a high-speed shearing and dispersing machine, the shearing and dispersing rotating speed is set at 2250-2350rpm (such as 2250rpm, 2280rppm, 2300rpm, 2320rpm or 2350 rpm) for 20-25min, and the mixture is kept stand for defoaming, and the sealed container is preserved in a light-resistant state.
For reference, the antimicrobial graft oligomer resin of the present application can be obtained by: and (3) carrying out reflux stirring reaction on polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, a solvent and a catalyst together, then adding pentaerythritol triacrylate, and continuing the reflux stirring reaction.
In some embodiments, the molar ratio of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, and pentaerythritol triacrylate is 1:2.05-2.1:1-1.05, such as 1:2.05:1, 1:2.05:1.01, 1:2.05:1.02, 1:2.05:1.03, 1:2.05:1.04, 1:2.05:1.05, 1:2.08:1, 1:2.08:1.01, 1:2.08:1.02, 1:2.08:1.03, 1:2.08:1.04, 1:2.08:1.05, 1:2.1:1, 1:2.1:1.01, 1:2.1:1.02, 1:2.1:1.04, 1:2.1:1.05, etc., as well as other values within the range of 1:2.05-2.1.05 to 1.05 are possible.
In some embodiments, the solvent used to prepare the antimicrobial grafted oligomer resin is ethyl acetate. The mass of the solvent was 50% of the total mass of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, and pentaerythritol triacrylate.
In some embodiments, the catalyst used to prepare the antimicrobial grafted oligomer resin is dibutyltin dilaurate. The mass of the catalyst is 0.01-0.012% of the total mass of polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate and pentaerythritol triacrylate, such as 0.01%, 0.011% or 0.012%, and the catalyst can be any other value within the range of 0.01-0.012%.
In some embodiments, the reflux stirring reaction prior to addition of pentaerythritol triacrylate is performed at 70-80℃ (e.g., 70℃, 72℃, 75℃, 78℃, 80℃, etc.) for 3-3.5 hours. The reflux stirring time after the pentaerythritol triacrylate is added is 4-4.5h.
Further, after the whole reflux stirring reaction is finished, the temperature is reduced to room temperature, and then a solvent (ethyl acetate) is added to dilute the antibacterial agent grafted oligomer resin to a solid content of 50wt%.
In addition, the application also provides a skin-feel film (also can be a skin-feel coating) which is prepared from the skin-feel coating.
Correspondingly, the application also provides a preparation method of the skin feel film, which comprises the following steps: and (3) coating the skin-feel coating on the surface of the PET film, drying, curing by UV light irradiation, and rolling.
Preferably, the solids content of the skin feel coating applied to the surface of the PET film is 25wt%.
For reference, the temperatures in the various zones of the oven used for drying are as follows: the first region is 42-48deg.C, the second region is 72-78deg.C, the third region is 87-93deg.C, the fourth region is 97-103 deg.C, the fifth region is 87-93 deg.C, and the sixth region is 77-83 deg.C.
In some preferred embodiments, the oven temperatures used for drying are as follows: the first zone is 45 ℃, the second zone is 75 ℃, the third zone is 90 ℃, the fourth zone is 100 ℃, the fifth zone is 90 ℃, and the sixth zone is 80 ℃.
In some embodiments, the UV light energy is 400-500mj/cm during the preparation of the skin feel film 2 Such as 400mj/cm 2 、420mj/cm 2 、450mj/cm 2 、480mj/cm 2 Or 500mj/cm 2 Etc. may be 400-500mj/cm 2 Any other value within the range.
In some embodiments, the coating speed is 15m/min during the skin feel film preparation process.
Specifically, the skin-feel paint can be diluted with ethyl acetate to a preset solid content, then dispersed for 10min (the rotating speed is 500 rpm) by a shearing and dispersing machine, and filtered by 300-mesh filter cloth after standing and defoaming, and sealed for later use. The PET film with the thickness of 36-100 mu m after the precoating treatment is placed on an unreeling frame of a coating machine, a micro-concave roller is used for coating and gluing, the temperature of each area of a baking oven is set to be 45+/-3 ℃ in one area, 75+/-3 ℃ in two areas, 90+/-3 ℃ in three areas, 100+/-3 ℃ in four areas, 90+/-3 ℃ in five areas and 80+/-3 ℃ in six areas, and the UV light energy is set to be 400-500mj/cm 2 . The coating speed is 15m/min, the thickness of the dry adhesive is controlled to be 6-8 mu m, and the PET skin-feel film can be prepared by rolling, slitting, inspecting and packaging.
It should be noted that, other preparation processes, conditions, principles, etc. of the skin feel film not described in detail in the present application may refer to related prior art, and are not described in detail herein.
The skin-feel film can be used as a surface film of a household decorative plate.
The features and capabilities of the present application are described in further detail below in connection with the examples.
Example 1
The embodiment provides a PET skin feel film with antibacterial and antifouling functions, which is prepared by the following method:
step (1): an antimicrobial grafted oligomer resin is prepared.
Polyhexamethylene guanidine hydrochloride (PHMG) and Hexamethylene Diisocyanate (HDI) were mixed according to 1:2.05, adding the mixture into a 500mL four-necked flask, adding 50% of ethyl acetate of the total mass of three reactants (polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate and pentaerythritol triacrylate) as a solvent, controlling the temperature at 75+/-5 ℃, adding dibutyltin dilaurate of which the total mass is 0.01% of the total mass of the reactants as a catalyst, carrying out reflux stirring reaction for 3h, adding pentaerythritol triacrylate with the same mole number as HDI, and continuing the reflux stirring reaction for 4h. After cooling to room temperature, ethyl acetate is added to dilute the solid content to 50 weight percent, and the polyhexamethylene guanidine hydrochloride grafted pentaerythritol triacrylate oligomer resin (PHMG-HDI-PETA) is obtained.
Step (2): the skin-feel paint with the antibacterial and antifouling functions is prepared.
The following raw materials are dispersed and stirred uniformly in a light-resistant container (black container) according to the following parts by weight, the stirring speed is 2300rpm, and the stirring time is 20min, so that the skin-feel paint with the antibacterial and antifouling functions is prepared.
3 parts of antibacterial grafted oligomer resin (PHMG-HDI-PETA), 3.4 parts of fluorine-containing antifouling UV resin (UV-370), 3 parts of pentaerythritol tetraacrylate, 30 parts of polyurethane acrylate oligomer (CN 9002), 2 parts of photoinitiator (JCCURE 184), 8 parts of spherical silica micropowder (HM 051 HM), 0.5 part of hand feeling slip agent (SY-905), 0.1 part of dispersing agent (BYK 361N) and 50 parts of diluent (ethyl acetate).
Step (3): PET skin feel film was prepared.
Metering the skin-feel coating prepared in the step (2), diluting the skin-feel coating with ethyl acetate to obtain a skin-feel coating liquid with the solid content of 25wt%, dispersing the skin-feel coating liquid for 10min (the rotating speed is 500 rpm) by a shearing dispersing machine, standing for defoaming, filtering the skin-feel coating liquid by using 300-mesh filter cloth, and sealing the skin-feel coating liquid for later use. The PET film with the thickness of 50 mu m after the precoating treatment is placed on an unreeling frame of a coating machine, the coating sizing is carried out by a micro-concave roller, the temperature of each area of a baking oven is set to be 45 ℃ in one area, 75 ℃ in two areas, 90 ℃ in three areas, 100 ℃ in four areas, 90 ℃ in five areas and 80 ℃ in six areas, and the UV light energy is set to be 400mj/cm 2 . Coating speed is 15m/min, the thickness of the dry adhesive is controlled to be 6 mu m, and the PET skin-feel film is prepared by rolling, slitting, inspecting and packaging.
Example 2
This example differs from example 1 in that the skin feel coating was prepared from the following raw materials:
4 parts of antibacterial agent grafted oligomer resin (PHMG-HDI-PETA), 3.1 parts of fluorine-containing antifouling UV resin (Lucure 8696), 5 parts of pentaerythritol tetraacrylate, 26 parts of polyurethane acrylate oligomer (6196-100), 2 parts of photoinitiator (Irgacure 819), 9 parts of spherical silica micropowder (ML-SiO 2 -H20), 0.7 parts of a hand slip agent (XH-a 51), 0.2 parts of a dispersant (BYK 361N) and 50 parts of a diluent (ethyl acetate).
Example 3
This example differs from example 1 in that the skin feel coating was prepared from the following raw materials:
5 parts of an antibacterial grafted oligomer resin (PHMG-HDI-PETA), 2 parts of a fluorine-containing antifouling UV resin (HYR-7935), 3.2 parts of pentaerythritol tetraacrylate, 28.1 parts of polyurethane acrylate oligomer (Agisyn 2423), 2.1 parts of a photoinitiator (Omnirad TPO), 8.8 parts of spherical silica micropowder (HM 051 HM), 0.65 part of a hand feeling slip agent (SY-905), 0.15 part of a dispersing agent (BYK 361N) and 50 parts of a diluting agent (ethyl acetate).
Example 4
This example differs from example 1 in that the skin feel coating was prepared from the following raw materials:
4.2 parts of an antimicrobial grafted oligomer resin (PHMG-HDI-PETA), 3.0 parts of a fluorine-containing anti-fouling UV resin (UV-370), 4 parts of pentaerythritol tetraacrylate, 28 parts of a polyurethane acrylate oligomer (CN 9002: agisyn=1:1), 2 parts of a photoinitiator (JRCURE 184), 8 parts of spherical silica micropowder (HM 051HM: ML-SiO) 2 H20=1:1), 0.6 parts of hand slip agent (SY-905), 0.2 parts of dispersant (BYK 361N) and 50 parts of diluent (ethyl acetate).
Example 5
This example differs from example 1 in that the skin feel coating was prepared from the following raw materials:
5 parts of an antimicrobial grafted oligomer resin (PHMG-HDI-PETA), 2 parts of a fluorine-containing anti-fouling UV resin (Lucure 8696), 5 parts of pentaerythritol tetraacrylate, 27.2 parts of a polyurethane acrylate oligomer (CN 9002:6196-100=1:1), 2 parts of a photoinitiator (JCCURE 184:Irgacure 819=1:1), 8 parts of spherical silica micropowder (HM051 HM: ML-SiO) 2 H20=1:1), 0.6 parts of hand slip agent (SY-905), 0.2 parts of dispersant (BYK 361N) and 50 parts of diluent (ethyl acetate).
Example 6
This example differs from example 1 in that the conditions for preparing the PET skin feel film are as follows:
metering the skin-feel coating prepared in the step (2), diluting the skin-feel coating with ethyl acetate to obtain a skin-feel coating liquid with the solid content of 25wt%, dispersing the skin-feel coating liquid for 10min (the rotating speed is 500 rpm) by a shearing dispersing machine, standing for defoaming, filtering the skin-feel coating liquid by using 300-mesh filter cloth, and sealing the skin-feel coating liquid for later use. 100 μm after precoating treatmentThe PET film of (2) is placed on an unreeling frame of a coating machine, a micro-concave roller is used for coating and gluing, the temperature of each area of a baking oven is set to be one area 42 ℃, two areas 72 ℃, three areas 87 ℃, four areas 97 ℃, five areas 87 ℃, six areas 77 ℃, and the UV light energy is set to be 450mj/cm 2 . Coating speed is 15m/min, the thickness of the dry adhesive is controlled to be 5 mu m, and the PET skin-feel film is prepared by rolling, slitting, inspecting and packaging.
Example 7
This example differs from example 1 in that the conditions for preparing the PET skin feel film are as follows:
metering the skin-feel coating prepared in the step (2), diluting the skin-feel coating with ethyl acetate to obtain a skin-feel coating liquid with the solid content of 25wt%, dispersing the skin-feel coating liquid for 10min (the rotating speed is 500 rpm) by a shearing dispersing machine, standing for defoaming, filtering the skin-feel coating liquid by using 300-mesh filter cloth, and sealing the skin-feel coating liquid for later use. The PET film with the thickness of 36 mu m after the precoating treatment is placed on an unreeling frame of a coating machine, the coating sizing is carried out by a micro-concave roller, the temperature of each area of a baking oven is set to be 48 ℃ in one area, 78 ℃ in two areas, 93 ℃ in three areas, 103 ℃ in four areas, 93 ℃ in five areas and 83 ℃ in six areas, and the UV light energy is set to be 500mj/cm 2 . Coating speed is 15m/min, the thickness of the dry adhesive is controlled at 7 mu m, and the PET skin-feel film is prepared by rolling, slitting, inspecting and packaging.
Comparative example 1
This comparative example differs from example 1 in that the raw materials for the preparation of the skin feel coating do not contain an antimicrobial grafted oligomer resin (PHMG-HDI-PETA).
Comparative example 2
The difference between this comparative example and example 1 is that the raw material for preparing the skin-feel coating material does not contain fluorine-containing anti-fouling UV resin (UV-370).
Comparative example 3
The difference between this comparative example and example 1 is that the raw materials for preparing the skin-feel coating material do not contain spherical silica micropowder (HM 051 HM) and a hand feeling slip agent (SY-905).
Comparative example 4
This comparative example differs from example 1 in that the antibacterial graft oligomer resin (PHMG-HDI-PETA) was replaced with an equivalent amount of PHMB (polyhexamethylene biguanide hydrochloride).
Comparative example 5
This comparative example differs from example 1 in that the fluorine-containing anti-fouling UV resin (UV-370) was replaced by an equivalent amount of B-868 (Boxing New Material technology Co., ltd.).
Comparative example 6
This comparative example differs from example 1 in that the spherical silica fine powder (HM 051 HM) was replaced with an equal amount of fumed silica 974 (win-desquamation (chinese) limited).
Comparative example 7
This comparative example differs from example 1 in that the hand slip agent (SY-905) is replaced by an equivalent amount of erucamide.
Comparative example 8
This comparative example differs from example 1 in that the amount of the antimicrobial graft oligomer resin (PHMG-HDI-PETA) used was 8 parts, and correspondingly, the diluent was reduced by 5 parts.
Comparative example 9
The difference between this comparative example and example 1 is that the amount of fluorine-containing anti-fouling UV resin (UV-370) used was 5 parts, and correspondingly, the diluent was reduced by 1.6 parts.
Comparative example 10
The difference between this comparative example and example 1 is that the amount of spherical silica micropowder (HM 051 HM) used was 10 parts, and the corresponding diluent was reduced by 2 parts.
Comparative example 11
The difference between this comparative example and example 1 is that the amount of the hand slip agent (SY-905) used was 1 part, and the corresponding diluent was reduced by 0.5 part.
Comparative example 12
The present comparative example is different from example 1 in that the antibacterial agent PHMG (polyhexamethylene guanidine hydrochloride) was obtained by mechanical blending of raw materials, and no chemical bonding was performed.
Test examples
The following measurements were made on the skin feel coatings prepared in examples 1-7 and comparative examples 1-12 with PET skin feel films: the skin-feel coating on one side of the PET skin-feel film is used for measuring the antibacterial validity period, the inhibition rate of gram-negative escherichia coli, the inhibition rate of gram-positive staphylococcus aureus and the antifouling effect of the marker pen; the PET skin feel film was evaluated for surface hardness, wear number, glossiness, friction coefficient and appearance and hand feel.
Wherein, antibacterial property measurement: antibacterial performance detection is carried out according to GB/T21866-2008 antibacterial paint (paint film) antibacterial test assay and antibacterial effect, and the used strain samples are gram-negative escherichia coli and gram-positive staphylococcus aureus;
determination of antifouling effect: testing according to national standard GB/T17657-2013 method for testing physicochemical Properties of Artificial Board and veneer Artificial Board;
surface pencil hardness determination: according to the national standard GB/T6739-2006 "color paint and varnish: the pencil method is used for measuring the hardness of a paint film, and the surface hardness of one side of the skin feel coating of the decorative film is measured;
wear-resistant times measurement: according to national standard GB/T17657-2013 method for testing physicochemical properties of artificial boards and decorative artificial boards, a Taber type abrasion resistance instrument or an abrasion resistance instrument with similar functions is adopted;
gloss measurement: 20 of a paint film of a paint and varnish free of metallic pigments according to the national standard GB/T9754-2007 ° 、60 ° And 85 ° Measurement of specular gloss, 60 is selected ° And (5) angle measurement.
The test results are shown in Table 1.
TABLE 1 Performance test results
As can be seen from table 1: the skin-feel coating and the skin-feel film (examples 1 to 7) with the antibacterial and antifouling functions prepared by adopting the scheme of the application have long-acting antibacterial effective period, have good inhibition rate on escherichia coli and staphylococcus, have obvious antifouling effect, are extremely easy to remove stains, and have better surface hardness and wear resistance. The skin-feel coating of comparative example 1 does not contain an antibacterial agent grafted oligomer resin, the skin-feel coating of comparative example 2 does not contain fluorine-containing antifouling UV resin, the skin-feel coating of comparative example 3 does not contain spherical silica micropowder and a hand feeling slip agent, and the corresponding antibacterial effective period, the inhibition rate to escherichia coli, the inhibition rate to staphylococcus, the antifouling effect, the appearance hand feeling effect and the like are all inferior to those of examples 1-7.
As can be seen from comparative examples 1 to 7 and comparative example 1: the skin-feel coating containing the antibacterial agent grafted oligomer resin can obviously improve the antibacterial performance of the PET skin-feel film, the antibacterial effective period is more than or equal to 5 years, and the antibacterial agent grafted oligomer resin has good inhibition rate on escherichia coli and staphylococcus; whereas comparative example 1 had no antibacterial effect. As can be seen from comparative examples 1 to 7 and comparative example 2: the skin feel coating containing the anti-fouling UV resin had a remarkable anti-fouling function, whereas the skin feel coating of comparative example 2 containing no anti-fouling resin had no anti-fouling function. As can be seen from comparative examples 1 to 7 and comparative example 3: the skin-feel film with the antibacterial and antifouling functions has the matte and skin-friendly smooth hand feel effects, while the comparative example 3 does not contain spherical silica micropowder and the hand feel slip agent, and the corresponding skin-feel film does not have the matte and skin-friendly smooth hand feel effects.
As can be seen from comparative example 1 and comparative examples 4 to 7: the antibacterial or antifouling or matte or skin-friendly substances are not adopted at random, so that the better effect can be obtained correspondingly. The antibacterial effective period of the skin-feel coating of the comparative example 4 is less than or equal to 2 years; the skin feel coating of comparative example 5 has reduced antifouling effect and is not easy to wipe; the abrasion resistance of the skin feel film of comparative example 6 is reduced to 100 times, and the hand feel is not smooth; the abrasion resistance of the skin feel film of comparative example 7 was reduced to 50 times, and the hand feel was not smooth.
As can be seen from comparative example 1 and comparative examples 8 to 11: the raw materials in the application need to be in a specific proportion to enable the final skin feel film to have excellent effect. The abrasion resistance of the skin feel film of comparative example 8 was reduced to 100 times, and the gloss was increased to 15GU; comparative example 9 the gloss of the skin feel film increased to 20GU; comparative example 10 skin feel film abrasion resistance was reduced to 100 times; comparative example 11 skin feel film abrasion resistance was reduced to 100 times.
As can be seen from comparative example 1 and comparative example 12: compared with the conventional antibacterial agent blending method, the antibacterial agent prepared by adopting the chemical bonding method can greatly prolong the antibacterial function of the skin-feel coating. The antibacterial effective period of the skin-feel coating of the comparative example 12 is shortened to less than or equal to 2 years.
In conclusion, the antibacterial grafted oligomer resin and the fluorine-containing antifouling UV resin contained in the skin-feel coating provided by the application can endow the skin-feel coating with excellent antibacterial antifouling functions, and the duration of action is long. The spherical silica micropowder and the hand feeling slip agent can endow the skin feel film with excellent matte effect and smooth hand feeling.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (19)
1. The skin-feel coating is characterized in that the raw materials for preparing the skin-feel coating consist of 3-5 parts by weight of antibacterial agent grafted oligomer resin, 2-3.4 parts by weight of fluorine-containing antifouling UV resin, 3-5 parts by weight of pentaerythritol tetraacrylate, 26-30 parts by weight of polyurethane acrylate oligomer, 2-2.1 parts by weight of photoinitiator, 8-9 parts by weight of spherical silica micropowder, 0.5-0.7 part by weight of hand feeling slip agent, 0.1-0.2 part by weight of BYK361N and 50 parts by weight of diluent;
the antibacterial agent grafted oligomer resin is obtained by carrying out addition polymerization reaction on polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate and pentaerythritol triacrylate;
the photoinitiator is selected from at least one of JRCURE184, irgacure819 and Omnirad TPO; the fluorine-containing anti-fouling UV resin is selected from at least one of UV-370, lucure8696 and HY-R7935; the polyurethane acrylate oligomer is selected from at least one of CN9002, 6196-100 and Agisyn 2423; the spherical silica micropowder is selected from HM051HM and ML-SiO 2 -at least one of H2O; the hand feeling slip agent is at least one selected from SY-905 and XH-A51.
2. A method of preparing a skin feel coating according to claim 1, comprising the steps of: mixing the raw materials according to the proportion.
3. The preparation method according to claim 2, wherein each raw material is initially stirred, left to stand until the spherical silica micropowder is sufficiently wetted, then mixed for 20-25min under the condition of shearing dispersion rotation speed of 2250-2350rpm, and left to stand for defoaming.
4. The method of claim 2, wherein the antimicrobial grafted oligomer resin is obtained by: and (3) carrying out reflux stirring reaction on polyhexamethylene guanidine hydrochloride, hexamethylene diisocyanate, a solvent and a catalyst together, then adding pentaerythritol triacrylate, and continuing the reflux stirring reaction.
5. The method according to claim 4, wherein the molar ratio of the polyhexamethylene guanidine hydrochloride, the hexamethylene diisocyanate, and the pentaerythritol triacrylate is 1:2.05-2.1:1-1.05.
6. The method according to claim 4, wherein the solvent is ethyl acetate.
7. The method according to claim 6, wherein the mass of the solvent is 50% of the total mass of the polyhexamethylene guanidine hydrochloride, the hexamethylene diisocyanate, and the pentaerythritol triacrylate.
8. The method according to claim 4, wherein the catalyst is dibutyltin dilaurate.
9. The production method according to claim 8, wherein the mass of the catalyst is 0.01 to 0.012% of the total mass of the polyhexamethylene guanidine hydrochloride, the hexamethylene diisocyanate, and the pentaerythritol triacrylate.
10. The process according to claim 4, wherein the reflux stirring reaction before the pentaerythritol triacrylate is carried out at 70 to 80℃for 3 to 3.5 hours.
11. The method according to claim 10, wherein the reflux stirring time after adding pentaerythritol triacrylate is 4 to 4.5 hours.
12. The process of claim 4, wherein the solvent is added to dilute the antimicrobial graft oligomer resin to a solids content of 50wt% after the entire reflux stirring reaction is completed.
13. A skin feel film, characterized in that it is prepared from the skin feel coating according to claim 1.
14. The method of preparing a skin feel film according to claim 13, wherein the preparation of the skin feel film comprises the steps of: and coating the skin-feel coating on the surface of the PET film, drying, curing by UV light irradiation, and rolling.
15. The method of claim 14, wherein the skin feel coating applied to the surface of the PET film has a solids content of 25wt%.
16. The method of claim 15, wherein the oven zones used for drying are at the following temperatures: the first region is 42-48deg.C, the second region is 72-78deg.C, the third region is 87-93deg.C, the fourth region is 97-103 deg.C, the fifth region is 87-93 deg.C, and the sixth region is 77-83 deg.C.
17. The method according to claim 14, wherein the UV light energy is 400-500mj/cm during the preparation of the skin-feel film 2 。
18. The method according to claim 14, wherein the coating speed is 15m/min during the preparation of the skin feel film.
19. The use of a skin feel film according to claim 13, wherein the skin feel film is used as a surface mount film for a household decorative board.
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| CN116004109A (en) | 2023-04-25 |
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