Super-hydrophobic resin, its preparation method and application

Abstract

The present application relates to the technical field of denture base material, and particularly relates to a super-hydrophobic resin and a preparation method and application thereof.The present application provides a super-hydrophobic resin, which comprises the following raw materials in mass fractions: 5-25 parts of low-surface-energy resin, 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-tenacity aliphatic polyurethane acrylate, 5-25 parts of monofunctional free radical acrylate monomer, 5-25 parts of bifunctional free radical acrylate monomer, 5-15 parts of trifunctional free radical acrylate monomer, 1.5-4.5 parts of colorant, 1-5 parts of photoinitiator and 0.1-1 part of additive.The super-hydrophobic resin has self-cleaning ability and excellent low-bacteria adhesion.

Description

Technical Field

[0001] This invention relates to the field of denture base materials technology, and in particular to a superhydrophobic resin, its preparation method and application. Background Technology

[0002] Surveys show that people over 65 years old have an average of 7.5 missing teeth, with 4.5% being edentulous. Many elderly people suffer from tooth loss or even complete edentulism. Statistics indicate that 26% of people over 55 years old worldwide wear removable dentures. Tooth loss is a significant factor affecting the quality of life for the elderly. However, improper denture cleaning can lead to denture stomatitis, also known as chronic atrophic candidiasis. Lesions often occur at the contact point between the palate mucosa and the denture, causing swelling, redness, and a shiny appearance, possibly accompanied by patchy pseudomembranes. The primary cause of white Candida plaque formation is the reduced saliva flow between the denture base and the supporting mucosa. This significantly decreases the ability of saliva to wash away bacteria adhering to the teeth and oral soft tissues, severely impacting the self-cleaning function of teeth and oral tissues, thus leading to plaque formation and adhesion.

[0003] Currently, there are three main methods for cleaning denture bases: 1. Physical cleaning: Patients use a toothbrush, toothpaste, and water to clean the surface of the base. While simple and convenient, this method can easily cause wear and tear on the base, increasing surface roughness and making it easier for bacteria to adhere. 2. Chemical cleaning: This involves soaking the base in a peroxide solution. Although peroxide cleaners have good bactericidal effects, long-term use can irritate the eyes and mucous membranes, so they should be used with caution. 3. Adding antibacterial agents to the denture base: Current research has found that only antibacterial components distributed on the surface of the base are effective, and the amount added needs to be strictly controlled. Too little antibacterial effect will not be achieved, while too much will affect the mechanical strength of the base. In summary, all methods—physical, chemical, and antibacterial—have their shortcomings. Summary of the Invention

[0004] The purpose of this invention is to provide a superhydrophobic resin, its preparation method and application, wherein the superhydrophobic resin has self-cleaning ability and excellent low bacterial adhesion.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a superhydrophobic resin, comprising the following raw materials by weight: 5-25 parts of low surface energy resin, 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-toughness aliphatic polyurethane acrylate, 5-25 parts of monofunctional free radical acrylate monomer, 5-25 parts of difunctional free radical acrylate monomer, 5-15 parts of trifunctional free radical acrylate monomer, 1.5-4.5 parts of colorant, 1-5 parts of photoinitiator, and 0.1-1 parts of additives.

[0007] Preferably, the low surface energy resin comprises a fluorinated acrylic resin and / or an acrylate derivative containing a sesquioxane structure.

[0008] Preferably, the fluorinated acrylic resin comprises one or more of the following: trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, hexadecylfluorononyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, perfluoro-decyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, and 1H,1H-perfluorooctyl methacrylate.

[0009] The acrylate derivatives containing silsesquioxane structures include one or more of the following: methacryloyloxypropyl cage-like cage-like silsesquioxane, methacryloyloxypropyl ladder-like polysilsesquioxane, methacryloyloxypropyl heptaisobutyl cage-like polysilsesquioxane, and acryloyloxypropyl cage-like polysilsesquioxane.

[0010] Preferably, the high-strength aliphatic polyurethane acrylate includes one or more of dimethacrylate urethane, high-strength aliphatic polyurethane acrylate resin of type Uniclil R7496, and high-strength aliphatic polyurethane acrylate resin of type 230A2.

[0011] The high-toughness aliphatic polyurethane acrylate includes one or more of the following: high-toughness aliphatic polyurethane acrylate with model number U600, high-toughness aliphatic polyurethane acrylate with model number 8091, high-toughness aliphatic polyurethane acrylate with model number 8006, and high-toughness aliphatic polyurethane acrylate with model number 8881NS.

[0012] Preferably, the monofunctional free radical acrylate monomer includes one or more of cyclotrimethylolpropane acrylate, laurate acrylate, acrylmorpholine, dicyclopentenyl acrylate, isobornyl acrylate, ethoxyphenoxy acrylate, and ethoxynonylphenol acrylate.

[0013] The bifunctional free radical acrylate monomers include one or more of ethoxybisphenol A dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol diacrylate, tricyclodecanediethanol diacrylate, and dipropylene glycol diacrylate.

[0014] The trifunctional free radical acrylate monomers include one or more of the following: trimethylolpropane triacrylate, propoxylated glycerol triacrylate, trimethylolpropane trimethacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol triacrylate, and ethoxylated trimethylolpropane triacrylate.

[0015] Preferably, the photoinitiator includes photoacylphosphine oxide photoinitiators;

[0016] The photoinitiators of the photoacylphosphine oxide class include one or more of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide.

[0017] Preferably, the colorant includes inorganic colorant or organic color paste;

[0018] The inorganic pigments include one or more of titanium dioxide, iron oxide yellow, and iron oxide black;

[0019] The organic color paste includes one or more of the following: food-grade silica gel red paste, food-grade silica gel yellow paste, and food-grade silica gel blue paste.

[0020] Preferably, the additive includes one or more of polymerization inhibitors, defoamers, and viscosity modifiers;

[0021] The polymerization inhibitor includes p-hydroxyanisole and / or butylated hydroxytoluene;

[0022] The defoamers include defoamer with model number Sago-1667, defoamer with model number Sago-1886, and defoamer with model number Modaflow 9200;

[0023] The viscosity modifier includes fumed silica.

[0024] This invention also provides a method for preparing the superhydrophobic resin described in the above technical solution, comprising the following steps:

[0025] Under light-protected conditions, low surface energy resin, high-strength aliphatic polyurethane acrylate, high-toughness aliphatic polyurethane acrylate, monofunctional free radical acrylate monomer, difunctional free radical acrylate monomer, trifunctional free radical acrylate monomer, pigment, photoinitiator and additives are mixed and then subjected to 3D printing photocuring and secondary photocuring in sequence to obtain the superhydrophobic resin.

[0026] The present invention also provides the application of the superhydrophobic resin described in the above technical solution or the superhydrophobic resin prepared by the preparation method described in the above technical solution in the preparation of denture bases.

[0027] This invention provides a superhydrophobic resin, comprising the following raw materials by weight: 5-25 parts of low surface energy resin, 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-toughness aliphatic polyurethane acrylate, 5-25 parts of monofunctional free radical acrylate monomer, 5-25 parts of difunctional free radical acrylate monomer, 5-15 parts of trifunctional free radical acrylate monomer, 1.5-4.5 parts of colorant, 1-5 parts of photoinitiator, and 0.1-1 parts of additives. This invention uses a resin with low surface energy, polyurethane acrylate, acrylic monomer, and photoinitiator as raw materials to create a superhydrophobic resin with a contact angle greater than 155°, reducing bacterial adhesion and achieving antibacterial effects (resisting Candida albicans with a rate greater than 90%). Furthermore, by combining high-strength aliphatic polyurethane acrylate, high-toughness aliphatic polyurethane acrylate, monofunctional free radical acrylate monomers, difunctional free radical acrylate monomers, and trifunctional free radical acrylate monomers, the superhydrophobic resin exhibits excellent mechanical properties after curing during the preparation process. While its ultimate flexural strength exceeds 90 MPa, its maximum stress intensity factor for impact resistance exceeds 3 MPa·m. 1 / 2 It meets the requirements of denture base materials to be both rigid and tough. Detailed Implementation

[0028] This invention provides a superhydrophobic resin, comprising the following raw materials by weight: 5-25 parts of low surface energy resin, 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-toughness aliphatic polyurethane acrylate, 5-25 parts of monofunctional free radical acrylate monomer, 5-25 parts of difunctional free radical acrylate monomer, 5-15 parts of trifunctional free radical acrylate monomer, 1.5-4.5 parts of colorant, 1-5 parts of photoinitiator, and 0.1-1 parts of additives.

[0029] In this invention, unless otherwise specified, all raw materials used in the preparation are commercially available products well known to those skilled in the art.

[0030] The superhydrophobic resin of the present invention comprises, by weight, 5 to 25 parts of a low surface energy resin, preferably 10 to 20 parts, and more preferably 13 to 16 parts. In the present invention, the low surface energy resin preferably comprises a fluorinated acrylic resin and / or an acrylate derivative containing a silsesquioxane structure; the fluorinated acrylic resin comprises trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, heptafluorobutyl methacrylate, hexafluorobutyl acrylate, hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate, dodecafluoroheptyl methacrylate, hexadecylfluorononyl methacrylate, 2-(perfluorooctyl)ethyl methacrylate, perfluoro-n-decyl methacrylate, 2-(perfluorohexyl)ethyl methacrylate, and 2-(perfluorohexyl)ethyl methacrylate. The acrylate derivative comprises one or more of methyl methacrylate and 1H,1H-perfluorooctyl methacrylate, more preferably one or more of 2-(perfluorooctyl)ethyl methacrylate, hexafluorobutyl methacrylate, and dodecafluoroheptyl methacrylate; the acrylate derivative containing a silsesquioxane structure preferably includes methacryloyloxypropyl cage-like cage-like silsesquioxane (MAPOSS), methacryloyloxypropyl ladder-like polysilsesquioxane (MALPSQ), and methacryloyloxypropyl heptaisobutyl cage-like polysilsesquioxane (brand name: POSS302) and Acryloyloxypropyl cage-type polysilsesquioxane (brand name: One or more of the following (POS1013); when the low surface energy material is two or more of the above-mentioned specific selections, the present invention does not have any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio. In the present invention, the function of the low surface energy material is to reduce the surface energy of the resin system to achieve a superhydrophobic effect, thereby providing the product with self-cleaning ability and low bacterial adhesion performance.

[0031] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of this invention comprises 10-30 parts of high-strength aliphatic polyurethane acrylate, preferably 15-25 parts, and more preferably 18-22 parts. In this invention, the high-strength aliphatic polyurethane acrylate preferably comprises one or more of the following: dimethacrylate, Unicryl R7496 high-strength aliphatic polyurethane acrylate resin, and 230A2 high-strength aliphatic polyurethane acrylate resin; the Unicryl R7496 high-strength aliphatic polyurethane acrylate resin was purchased from Aurun Chemical; the 230A2 high-strength aliphatic polyurethane acrylate resin was purchased from Guangyi Chemical; when the high-strength aliphatic polyurethane acrylate comprises two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the proportion of the above-mentioned specific substances, and they can be mixed in any proportion. In this invention, the function of the high-strength aliphatic polyurethane acrylate is to provide the rigidity required for the product, so that the cured denture base has excellent strength and modulus.

[0032] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of this invention comprises 10-30 parts of high-toughness aliphatic polyurethane acrylate, preferably 15-25 parts, and more preferably 18-22 parts. In this invention, the high-toughness aliphatic polyurethane acrylate preferably includes one or more of the following: U600 high-toughness aliphatic polyurethane acrylate (purchased from Guangyi Chemical), 8091 high-toughness aliphatic polyurethane acrylate (purchased from Aorun Chemical), 8006 high-toughness aliphatic polyurethane acrylate (purchased from Aorun Chemical), and 8881NS high-toughness aliphatic polyurethane acrylate (purchased from Sartoma (Guangzhou) Chemical Co., Ltd.). When the high-toughness aliphatic polyurethane acrylate comprises two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the proportion of the above-mentioned substances; they can be mixed in any proportion. In this invention, the function of the high-toughness aliphatic polyurethane acrylate is to provide the required toughness for the product, enabling the cured denture base to have excellent impact resistance and fracture toughness.

[0033] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of this invention comprises 5-25 parts of monofunctional free radical acrylate monomers, preferably 10-20 parts, and more preferably 13-16 parts. In this invention, the monofunctional free radical acrylate monomers include one or more of cyclotrimethylolpropane acrylates, laurate acrylates, acryloylmorpholine, dicyclopentenyl acrylates, isobornyl acrylates, ethoxyphenoxy acrylates, and ethoxynonylphenol acrylates. When the monofunctional free radical acrylate monomers are two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the proportion of the above-mentioned substances; they can be mixed in any proportion. In this invention, the function of the monofunctional free radical acrylate monomers is to adjust the viscosity of the resin system, while reducing the curing shrinkage rate of the superhydrophobic resin during printing and improving the product's resistance to deformation.

[0034] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of this invention comprises 5-25 parts of bifunctional radical acrylate monomers, preferably 10-20 parts, and more preferably 13-16 parts. In this invention, the bifunctional radical acrylate monomers preferably include one or more of ethoxybisphenol A dimethacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol diacrylate, tricyclodecanediethanol diacrylate, and dipropylene glycol diacrylate. When the bifunctional radical acrylate monomers are two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the ratio of the above-mentioned substances; they can be mixed in any ratio. In this invention, the function of the bifunctional radical acrylate monomers is to increase the photocuring reaction rate of the superhydrophobic resin, provide excellent toughness to the product, and also have a certain dilution effect.

[0035] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of this invention comprises 5-15 parts of trifunctional free radical acrylate monomers, preferably 8-12 parts, and more preferably 10 parts. In this invention, the trifunctional free radical acrylate monomers include one or more of trimethylolpropane triacrylate, propoxylated glycerol triacrylate, trimethylolpropane trimethacrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, pentaerythritol triacrylate, and ethoxylated trimethylolpropane triacrylate. When the trifunctional free radical acrylate monomers are two or more of the above-mentioned specific selections, this invention does not impose any special limitation on the proportion of the above-mentioned substances; they can be mixed in any proportion. In this invention, the role of the trifunctional free radical acrylate monomers is to increase the curing crosslinking density and photocuring reaction rate of the superhydrophobic resin, providing the product with a certain degree of flexibility.

[0036] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of the present invention comprises 1.5 to 4.5 parts of colorant, preferably 2.0 to 4.0 parts, and more preferably 2.5 to 3.5 parts. In the present invention, the colorant preferably comprises inorganic colorant or organic color paste; the inorganic colorant preferably comprises one or more of titanium dioxide, iron oxide yellow, and iron oxide black; the organic color paste preferably comprises one or more of food-grade silicone red paste, food-grade silicone yellow paste, and food-grade silicone blue paste; when the colorant comprises two or more of the above-mentioned specific selections, the present invention does not impose any special limitation on the proportion of the above-mentioned specific substances, and they can be mixed in any proportion.

[0037] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of this invention comprises 1 to 5 parts of photoinitiator, preferably 2 to 4 parts, and more preferably 3 parts. In this invention, the photoinitiator preferably comprises a photoacylphosphine oxide photoinitiator; the photoacylphosphine oxide photoinitiator preferably comprises one or more of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide. When the photoinitiator is two or more of the above-mentioned specific selections, this invention does not have any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio. In this invention, the function of the photoinitiator is to decompose and generate active free radicals when the superhydrophobic resin is irradiated by a light source with a wavelength of 350-420 nm, thereby initiating a polymerization reaction in the resin.

[0038] Based on the mass fraction of the low surface energy resin, the superhydrophobic resin of the present invention comprises 0.1 to 1 part of additives, preferably 0.3 to 0.8 parts, and more preferably 0.4 to 0.6 parts. In the present invention, the additives preferably include one or more of a polymerization inhibitor, a defoamer, and a viscosity modifier; the polymerization inhibitor preferably includes p-hydroxyanisole and / or butylated hydroxytoluene; the defoamer preferably includes defoamer of type Sago-1667, defoamer of type Sago-1886, and defoamer of type Modaflow 9200; the viscosity modifier preferably includes fumed silica. When the additives are two or more of the above-mentioned specific selections, the present invention does not impose any special limitation on the ratio of the above-mentioned specific substances, and they can be mixed in any ratio. In this invention, the role of the polymerization inhibitor is to extend the shelf life of the resin system and prevent the resin from prepolymerizing during storage; the role of the defoamer is to eliminate air bubbles in the resin system and avoid affecting the printing effect; the role of the viscosity modifier is to control the viscosity of the resin system and prevent pigment sedimentation from occurring after prolonged storage.

[0039] This invention also provides a method for preparing the superhydrophobic resin described in the above technical solution, comprising the following steps:

[0040] Under light-protected conditions, low surface energy resin, high-strength aliphatic polyurethane acrylate, high-toughness aliphatic polyurethane acrylate, monofunctional free radical acrylate monomer, difunctional free radical acrylate monomer, trifunctional free radical acrylate monomer, pigment, photoinitiator and additives are mixed and then subjected to 3D printing photocuring and secondary photocuring in sequence to obtain the superhydrophobic resin.

[0041] In this invention, the mixing is preferably carried out under stirring conditions, and the stirring speed is preferably 1200-1500 rpm, more preferably 1250-1450 rpm, and most preferably 1300-1400 rpm. The stirring time is preferably 1-3 hours, more preferably 1.5-2.5 hours, and most preferably 1.8-2.2 hours. The mixing temperature is preferably 50-60°C, more preferably 52-58°C, and most preferably 54-56°C.

[0042] In this invention, the wavelength of the light source used for 3D printing photopolymerization is preferably 385nm or 405nm, and the temperature of the printing chamber is preferably 30-35℃, more preferably 31-34℃, and most preferably 32-33℃. In this invention, the function of 3D printing photopolymerization is to mold the resin into a denture base restoration, obtaining a high-precision printed part.

[0043] In this invention, the optical power of the secondary photocuring is preferably 50–200 mW / cm². 2 More preferably 80–160 mW / cm 2 The optimal value is 100–130 mW / cm². 2 In this invention, the secondary light curing function is to eliminate the stickiness on the denture base surface, increase surface hardness, and improve the denture base's scratch resistance and drop resistance.

[0044] This invention also provides the application of the superhydrophobic resin described in the above-described technical solutions or the superhydrophobic resin prepared by the preparation method described in the above-described technical solutions in the preparation of denture bases. This invention does not impose any special limitations on the method of application; any method skilled in the art can be used.

[0045] The following detailed description of the superhydrophobic resin, its preparation method, and its application provided by the present invention, with reference to specific embodiments, should not be construed as limiting the scope of protection of the present invention.

[0046] Example 1

[0047] Raw materials for preparation: 25 parts by weight of urethane dimethacrylate, 25 parts by weight of high-toughness aliphatic polyurethane acrylate (model 8091), 15 parts by weight of hexafluorobutyl methacrylate, 10 parts by weight of cyclotrimethylolpropane acrylate, 10 parts by weight of tricyclodecanediethanol diacrylate, 10 parts by weight of ethoxylated trimethylolpropane triacrylate, 2.5 parts by weight of 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide, 2 parts by weight of colorant (specifically 0.8 parts by weight of titanium dioxide, 0.6 parts by weight of food-grade silicone red paste, 0.4 parts by weight of food-grade silicone blue paste, and 0.2 parts by weight of iron oxide yellow), and 0.5 parts by weight of p-hydroxyanisole;

[0048] Preparation process: Under light-protected conditions, the raw materials were mixed according to the above-mentioned preparation method (50℃, 1400rpm, 2h), and then 3D printing was performed at a wavelength of 405nm. The heating function of the printing chamber was turned on, and hot air was circulated inside the 33℃ hot air blower. After the first curing, a second photocuring was performed (light source wavelength of 405nm, light power of curing chamber of 150mW / cm²). 2 (The time was 15 minutes) to obtain superhydrophobic resin.

[0049] Example 2

[0050] Raw materials for preparation: 3 parts urethane dimethacrylate, 27 parts high-toughness aliphatic polyurethane acrylate (model 8006), 15 parts dodecafluoroheptyl methacrylate, 10 parts isobornyl acrylate, 10 parts 1,6-hexanediol dimethacrylate, 10 parts pentaerythritol triacrylate, 2.5 parts 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide, 2 parts colorant (specifically 0.8 parts titanium dioxide, 0.6 parts food-grade silica gel red paste, 0.4 parts food-grade silica gel blue paste, and 0.2 parts iron oxide yellow), and 0.5 parts p-hydroxyanisole;

[0051] Preparation process: Under light-protected conditions, the raw materials were mixed according to the above-mentioned preparation method (55℃, 1450rpm, 1.5h), and then 3D printing was performed at a wavelength of 405nm. The heating function of the printing chamber was turned on, and hot air was circulated inside a 33℃ hot air blower. After the first curing, a second photocuring was performed (light source wavelength of 405nm, light power of curing chamber of 150mW / cm²). 2 (The time was 15 minutes) to obtain superhydrophobic resin.

[0052] Example 3

[0053] Raw materials for preparation: 21 parts of urethane dimethacrylate, 29 parts of high-toughness aliphatic polyurethane acrylate (model 8006), 18 parts of 2-(perfluorooctyl)ethyl methacrylate, 7 parts of isobornyl acrylate, 10 parts of 1,6-hexanediol dimethacrylate, 10 parts of pentaerythritol triacrylate, 2.5 parts of 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide, 2 parts of colorant (specifically 0.8 parts of titanium dioxide, 0.6 parts of food-grade silicone red paste, 0.4 parts of food-grade silicone blue paste, and 0.2 parts of iron oxide yellow), and 0.5 parts of p-hydroxyanisole;

[0054] Preparation process: Under light-protected conditions, the raw materials were mixed according to the above-mentioned preparation method (55℃, 1400rpm, 2h), and then 3D printing was performed at a wavelength of 405nm. The heating function of the printing chamber was turned on, and hot air was circulated inside the 33℃ hot air blower. After the first curing, a second photocuring was performed (light source wavelength of 405nm, light power of curing chamber of 150mW / cm²). 2 (The time was 15 minutes) to obtain superhydrophobic resin.

[0055] Test case

[0056] Contact angle testing method:

[0057] This experiment used a contact angle measuring instrument, model XWK-705B, for testing. The syringe needle was focused until the image was clear. A pre-prepared 3D-printed base sample (30mm × 30mm × 5mm) was placed on the worktable. The appropriate liquid volume was selected, and the dripping process began. An image was taken when the droplet first contacted the sample. The data was processed using a fully automated fitting method, and the contact angle was recorded.

[0058] Antibacterial test method:

[0059] This experimental method refers to the People's Republic of China Light Industry Standard QB / T 2591-2003 (Experimental Methods and Antibacterial Effects of Antibacterial Resins).

[0060] Fresh bacterial cultures, obtained after two consecutive subculturings within 24 hours, were used. One to two loopfuls of fresh bacteria were scraped from the culture medium using an inoculation loop and added to the culture medium. This was followed by sequentially making 10-fold dilutions, selecting a bacterial concentration of (5.0–10.0) × 10⁻⁶. 5 A CFU / mL dilution was prepared as a bacterial suspension for later use.

[0061] The antibacterial performance was evaluated using the film-coating method. Samples were placed in 90mm diameter petri dishes, and 100μL of bacterial suspension was dropped onto the surface of each sample. A polyethylene film was then placed over the sample, spread evenly, and incubated at 37℃ and RH > 90% for 1 hour. After incubation, 20mL of sterile physiological saline was added to each dish as eluent. The sample and the covering film were repeatedly washed, and the eluent was thoroughly mixed. After serial dilution, 100μL of the eluent was inoculated onto an agar plate. Candida albicans was cultured aerobically for 24 hours, and the colony count (CFU) was performed after another 24 hours of incubation. This experiment was repeated three times.

[0062] The antibacterial rate was calculated using the following formula based on the measured colony count:

[0063] R(%) = (B - C) / B × 100%

[0064] R—Antibacterial rate (%)

[0065] B—Average recovered bacterial count (CFU / plate) in blank control samples

[0066] Average recovered bacterial count (CFU / piece) of C-3D printed base material samples

[0067] Ultimate flexural strength test method:

[0068] The experimental method was performed in accordance with section 8.5.3.5 of YY 0270.1-2011 "Dental Base Polymers Part 1: Dental Base Polymers".

[0069] Test method for maximum stress intensity factor of impact-resistant materials:

[0070] The experimental method was performed in accordance with section 8.6 of YY 0270.1-2011 "Dental Base Polymers Part 1: Dental Base Polymers".

[0071] The test results are shown in Table 1:

[0072] Table 1. Contact angle and anti-Candida albicans rate of the superhydrophobic resins described in Examples 1-3

[0073]

[0074] As shown in Table 1, the contact angles of the superhydrophobic resins described in Examples 1-3 are all greater than 150°, meeting the performance indicators of superhydrophobic materials. Furthermore, the average number of recovered bacteria is significantly reduced, and the antibacterial rate calculated using the antibacterial rate formula is greater than 90%. According to the QB / T 2591-2003 standard, "antibacterial resins with an antibacterial rate of R≥90% can be reported as having antibacterial activity." Therefore, the material prepared in this invention has antibacterial activity due to its strong antibacterial adhesion. Moreover, the stronger the superhydrophobicity of the material, the better the antibacterial effect. This phenomenon can be explained by the surface contact area of ​​the superhydrophobic material. Because the rough structure of the superhydrophobic material surface is generally a micro-nano multi-scale structure similar to papillae, this micro-nano structure has large air pockets in the middle, greatly reducing the contact area between water droplets or bacteria and the surface. Because the contact area is negligible, there are no sites for adhesion, and bacteria on the surface can be easily washed away with water, thus achieving a good antibacterial effect.

[0075] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A superhydrophobic resin, characterized in that, The raw materials, by weight, are as follows: 5-25 parts of low surface energy resin, 10-30 parts of high-strength aliphatic polyurethane acrylate, 10-30 parts of high-toughness aliphatic polyurethane acrylate, 5-25 parts of monofunctional free radical acrylate monomer, 5-25 parts of difunctional free radical acrylate monomer, 5-15 parts of trifunctional free radical acrylate monomer, 1.5-4.5 parts of colorant, 1-5 parts of photoinitiator, and 0.1-1 parts of additives; The low surface energy resin is hexafluorobutyl methacrylate, dodecafluoroheptyl acrylate or 2-(perfluorooctyl)ethyl methacrylate; The high-strength aliphatic polyurethane acrylate is dimethacrylate urethane. The high-toughness aliphatic polyurethane acrylate is either high-toughness aliphatic polyurethane acrylate of type 8091 or high-toughness aliphatic polyurethane acrylate of type 8006. The monofunctional free radical acrylate monomer is a cyclotrimethylolpropane-type acrylate or isobornyl acrylate. The bifunctional free radical acrylate monomer is tricyclodecanediethanol diacrylate or 1,6-hexanediol dimethacrylate. The trifunctional free radical acrylate monomer is trimethylolpropane triacrylate, pentaerythritol triacrylate or ethoxylated trimethylolpropane triacrylate; The additive is one or more of the following: polymerization inhibitor, defoamer, and viscosity modifier.

2. The superhydrophobic resin as described in claim 1, characterized in that, The photoinitiator includes photoacylphosphine oxide photoinitiators; The photoinitiators of the photoacylphosphine oxide class include one or more of 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide.

3. The superhydrophobic resin as described in claim 1, characterized in that, The colorant includes inorganic colorant or organic color paste; The inorganic pigments include one or more of titanium dioxide, iron oxide yellow, and iron oxide black; The organic color paste includes one or more of the following: food-grade silica gel red paste, food-grade silica gel yellow paste, and food-grade silica gel blue paste.

4. The superhydrophobic resin as described in claim 1, characterized in that, The polymerization inhibitor includes p-hydroxyanisole and / or butylated hydroxytoluene; The defoamers include defoamer with model number Sago-1667, defoamer with model number Sago-1886, and defoamer with model number Modaflow 9200; The viscosity modifier includes fumed silica.

5. A method for preparing the superhydrophobic resin according to any one of claims 1 to 4, characterized in that, Includes the following steps: Under light-protected conditions, low surface energy resin, high-strength aliphatic polyurethane acrylate, high-toughness aliphatic polyurethane acrylate, monofunctional free radical acrylate monomer, difunctional free radical acrylate monomer, trifunctional free radical acrylate monomer, pigment, photoinitiator and additives are mixed and then subjected to 3D printing photocuring and secondary photocuring in sequence to obtain the superhydrophobic resin.

6. The use of the superhydrophobic resin according to any one of claims 1 to 4 or the superhydrophobic resin prepared by the preparation method according to claim 5 in the preparation of denture bases.

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