Hardness-adjustable photocuring isolation molded sheet for oral cavity and preparation method of photocuring isolation molded sheet

Abstract

The invention discloses a hardness-adjustable photocuring isolation molded sheet for oral cavity and a preparation method thereof, the hardness-adjustable photocuring isolation molded sheet comprises the following raw material components by weight: 64-85 parts of organosilane containing sulfydryl; 5-30 parts of an acrylic monomer; 5 to 10 parts of a photoinitiator; and 1-10 parts of modified silicon dioxide particles. The preparation method comprises the following steps: S1, mixing the raw material components according to the proportion to obtain a mixture; s2, placing the mixture in a mold; s3, the mold is subjected to light curing; and isolating and forming sheets are obtained. The prepared photocuring isolation forming sheet for the oral cavity is adjustable in hardness and variable in shape; and personalized customization of the structure and the function of the formed sheet can be realized on a treatment site according to specific requirements of the isolation formed sheet on mechanical properties, thicknesses, shapes, isolation effects and the like required by tooth disease treatment of different patients.

Description

Technical Field

[0001] The invention belongs to the field of biomedical polymer material photocuring molding technology and oral medical product preparation technology, and specifically relates to a new transparent photocuring silicone rubber isolation molding sheet for oral use with adjustable hardness and softness and a preparation method thereof. Background Art

[0002] Teeth are the hardest organs in the human body. Generally speaking, teeth are white and hard in texture. The various shapes of teeth are suitable for a variety of purposes, including tearing and grinding food. However, due to caries, periodontal disease, trauma, tumors, congenital malformations, physiological wear and tear, etc., the loss of tooth hard tissue or tooth body makes oral diseases one of the main types of human diseases, accounting for about 70%. As my country has the largest population in the world, there are hundreds of millions of patients who need treatment and repair. According to the data of the National Bureau of Statistics, by the end of 2022, there will be more than 280 million elderly people aged 60 and above in the country, accounting for 19.8% of the total population of the country, of which 210 million are 65 years old and above, accounting for 14.9% of the total population of the country. With the continuous emergence of the aging problem in society and the continuous intensification of the aging trend of the population, the proportion of patients with missing teeth is increasing. According to relevant data, the number of patients with missing teeth currently accounts for 80% of the number of elderly people. When the tooth body is defective or lost, it is necessary to go to the oral hospital for treatment, such as tooth extraction, filling or implant.

[0003] During the oral treatment process, the patient will secrete a large amount of saliva, and the dental drills and other tools used by medical staff will also spray a large amount of water to clean the patient's mouth. Water and saliva will affect the treatment work and increase the uncertainty of dental treatment. Therefore, when extracting and filling teeth for patients, isolation molding sheets are usually used to isolate and mold the local treatment area. At present, there are mainly three types of isolation molding sheets used clinically: rectangular molding sheets made of transparent polyester materials, bean curd molding sheets and ring molding sheets made of metal; among them, the advantages of polyester molding sheets are: good transparency, good isolation, and low price; the advantages of metal molding sheets are: high strength and good toughness; but the fixing effect of polyester molding sheets is not as good as that of metal molding sheets; and metal molding sheets are relatively expensive and opaque; at the same time, neither polyester molding sheets nor metal molding sheets can be customized according to the needs of different patients for dental disease treatment. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides an oral light-curing isolation molding sheet with adjustable hardness and a preparation method thereof; the light-curing isolation molding sheet has both high strength and high transparency; and is adjustable hardness and changeable shape; and can realize personalized customization of the structure and function of the molding sheet according to the specific requirements of mechanical properties, thickness, shape, isolation effect and other specific requirements of the isolation molding sheet for the treatment of dental diseases of different patients at the treatment site, thereby effectively realizing multiple uses and multiple functional expansions of a material.

[0005] In order to achieve the purpose of the present invention, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a light-cured isolation molding sheet for oral use with adjustable hardness and softness, comprising the following raw material components by weight:

[0007] 64-85 parts of organosilane containing mercapto group;

[0008] 5-30 parts of acrylic monomer;

[0009] 5-10 parts of photoinitiator;

[0010] 1-10 parts of modified silicon dioxide particles.

[0011] In some embodiments of the present invention, the mercapto-containing organosilane includes one or more of (3-mercaptopropyl)trimethoxysilane, 3-mercaptopropyl(dimethoxy)silane, and (3-mercaptopropyl)triethoxysilane.

[0012] In some embodiments of the present invention, the acrylic monomer includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, hydroxypropyl (meth)acrylate, n-butyl acrylate, cyclohexyl methacrylate, diethylene glycol diacrylate, and 9-anthracenemethyl acrylate.

[0013] In some embodiments of the present invention, the photoinitiator includes one or more of monoketone and diketone; preferably, the diketone includes one or more of camphorquinone, benzil, furil, phenanthrenequinone, 1-phenyl-1,2-propanedione.

[0014] In some embodiments of the present invention, the modified silica particles include: one or more of amino-modified, carboxyl-modified and hydroxyl-modified silica particles; preferably, the shape structure of the modified silica particles includes one or more of solid, mesoporous, hollow mesoporous, multi-level porous, dendritic, nanowires, etc.; more preferably, the particle size of the modified silica particles is 20nm-5μm.

[0015] In some embodiments of the present invention, the light curing method is: UV curing; preferably, the irradiation intensity of UV curing is 70-120 mW / cm 2 ; More preferably, the irradiation time of UV curing is 5-20s.

[0016] In some embodiments of the present invention, the Shore hardness of the photocurable isolation molding sheet is 30A-80A, preferably 34A-80A, and more preferably 34A-78A.

[0017] In some embodiments of the present invention, the transparency of the photocurable isolation molding sheet is 60%-95%, preferably 63%-95%, and more preferably 63%-93%.

[0018] In a second aspect, the present invention provides a method for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness, comprising the following steps:

[0019] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0020] S2, placing the mixture in a mold;

[0021] S3, photocuring the mold to obtain an isolation molding sheet.

[0022] In the method for preparing the oral light-curing isolation molding sheet with adjustable hardness and softness of the present invention, the shape of the mold includes one or more of a rectangular shape, a bean-shaped shape, and a ring shape.

[0023] In the method for preparing the oral light-curable isolation molding sheet with adjustable hardness and softness of the present invention, the light curing is ultraviolet light curing. Preferably, the irradiation intensity of the ultraviolet light curing is 70-120 mW / cm 2 ; More preferably, the irradiation time of UV curing is 5-20s.

[0024] In a third aspect, the present invention provides an application of an oral light-curable isolation molding sheet with adjustable hardness or an isolation molding sheet prepared by the preparation method of the oral light-curable isolation molding sheet with adjustable hardness in oral treatment; preferably, the application in oral treatment includes application in dental restoration and dental products.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. Compared with conventional polyester or metal-based isolation molding sheets, the light-cured isolation molding sheet of the present invention has both high strength and high transparency; and its hardness and shape are adjustable.

[0027] 2. The present invention uses mercapto-containing organic silane and acrylic monomers, and adds an appropriate amount of silica particles to carry out a photocuring reaction to prepare a photocurable isolation molding sheet. The reaction does not require the use of solvents, has a fast reaction speed, high directional selectivity, mild reaction conditions, strong reaction adaptability, and low cost.

[0028] 3. The light-cured isolation molding sheet prepared by the present invention can realize personalized customization of the molding sheet structure and function at the treatment site according to the specific requirements of different patients for the mechanical properties, thickness, shape, isolation effect and other specific requirements of the isolation molding sheet for the treatment of dental diseases. Description of the drawings:

[0029] Figure 1 This is a photo of the harder ring-shaped photocurable isolation molding sheet prepared in Example 1;

[0030] Figure 2 This is a photograph of the relatively soft ring-shaped photocurable isolation molding sheet prepared in Example 6;

[0031] Figure 3 This is a photograph of a rectangular photocurable isolation molding sheet with moderate hardness and softness prepared in Example 5. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. Some non-essential improvements and adjustments made by technicians in this field based on the content of the present invention should be regarded as the protection scope of the present invention.

[0033] The inventors have found through research that the use of mercapto-containing organic silane and acrylic monomers, and the addition of an appropriate amount of silica particles for photocuring reaction to prepare a light-cured isolation molding sheet for oral use can achieve adjustable hardness and shape, and have both high strength and high transparency; at the treatment site, the structure and function of the molding sheet can be customized according to the specific needs of different patients for the treatment of dental diseases.

[0034] Based on the above viewpoints, the present invention provides a light-cured isolation molding sheet for oral use with adjustable hardness and softness, which comprises the following raw material components by weight:

[0035] 64-85 parts of organosilane containing mercapto group;

[0036] 5-30 parts of acrylic monomer;

[0037] 5-10 parts of photoinitiator;

[0038] 1-10 parts of modified silicon dioxide particles.

[0039] In some embodiments of the present invention, the mercapto-containing organosilane includes mercapto silanization agents, mercaptosilane oligomers and mercaptosiloxanes commonly used in the art; specifically, it includes one or more of (3-mercaptopropyl)trimethoxysilane, 3-mercaptopropyl (dimethoxy) silane, and (3-mercaptopropyl)triethoxysilane.

[0040] In some embodiments of the present invention, the acrylic monomer includes common acrylic ester monomers in the art; specifically, it includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, hydroxypropyl (meth)acrylate, n-butyl acrylate, cyclohexyl methacrylate, diethylene glycol diacrylate, and 9-anthracenemethyl acrylate.

[0041] In some embodiments of the present invention, the photoinitiator can be a conventional photoinitiator in the art, including one or more of monoketones and diketones; preferably, the diketone includes one or more of camphorquinone, benzil, furil, phenanthrenequinone, and 1-phenyl-1,2-propanedione.

[0042] In some embodiments of the present invention, the modification method of the modified silica particles is a common modification method in the art, which can improve the compatibility with other compounds and enhance the strength of the prepared light-cured isolation molding sheet. The modified silica particles include one or more of amino-modified, carboxyl-modified and hydroxyl-modified silica particles; preferably, the shape structure of the modified silica particles includes one or more of solid, mesoporous, hollow mesoporous, multi-level pores, dendritic, nanowires, etc.; more preferably, the particle size of the modified silica particles is 20nm-5μm.

[0043] In some embodiments of the present invention, the light curing method is a common light curing method in the art, and ultraviolet light curing is preferably used from the perspective of personalized customization. Preferably, the irradiation intensity of ultraviolet light curing is 70-120 mW / cm 2 ; More preferably, the irradiation time of UV curing is 5-20s.

[0044] In some embodiments of the present invention, from the perspective of personalized customization, the Shore hardness of the photocurable isolation molding sheet is 30A-80A; preferably 34A-80A; more preferably 34A-78A.

[0045] In some embodiments of the present invention, from the perspective of personalized customization, the transparency of the photocurable isolation molding sheet is 60%-95%, preferably 63%-95%, and more preferably 63%-93%.

[0046] In addition, the present invention provides a method for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness, comprising the following steps:

[0047] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0048] S2, placing the mixture in a mold;

[0049] S3, photocuring the mold to obtain an isolation molding sheet.

[0050] In the method for preparing the oral light-curing isolation molding sheet with adjustable hardness and softness of the present invention, the shape of the mold has no fixed shape. From the perspective of actual oral use, the shape of the mold includes one or more of a rectangular, bean-shaped, and a ring-shaped.

[0051] In the method for preparing the soft and hard adjustable oral light-curable isolation molding sheet of the present invention, the light curing is a common light curing method in the art, preferably ultraviolet light curing; further preferably, the irradiation intensity of the ultraviolet light curing is 70-120 mW / cm 2 ; More preferably, the irradiation time of UV curing is 5-20s.

[0052] The present invention also provides an application of the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness or the isolation molding sheet prepared by the preparation method of the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness in oral treatment; preferably, the application in oral treatment includes application in dental restoration and dental products.

[0053] Each photocurable isolation molding sheet of the present invention is tested by the following method:

[0054] Shore Hardness: Hardness is measured using a Shore durometer.

[0055] Transparency: The transmittance was tested at 550nm using a UV spectrophotometer.

[0056] The beneficial effects of the present invention will be further described below in conjunction with the embodiments and comparative examples. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0057] The manufacturers and brands of the raw materials used in Examples 1-6 of the present invention and Comparative Examples 1-2 are shown in Table 1.

[0058] Table 1

[0059]

[0060]

[0061] Example 1

[0062] Preparation of modified silica particles

[0063] The solid silica particles are amino-modified to obtain amino-modified solid silica particles with a particle size of 20 nm.

[0064] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0065]

[0066] The particle size of the amino-modified solid silica particles is 20 nm.

[0067] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0068] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0069] S2, placing the mixture in a ring-shaped mold;

[0070] S3, UV curing the ring-shaped mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0071] UV curing conditions are as follows: irradiation intensity is 70mW / cm 2 , curing for 20 seconds.

[0072] Example 2

[0073] Preparation of modified silica particles

[0074] The mesoporous silica particles are carboxyl-modified to obtain carboxyl-modified mesoporous silica particles with a particle size of 75 nm.

[0075] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0076]

[0077] The particle size of the carboxyl-modified mesoporous silica particles is 75 nm.

[0078] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0079] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0080] S2, placing the mixture in a rectangular mold;

[0081] S3, UV-curing the rectangular mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0082] UV curing conditions are as follows: irradiation intensity is 80mW / cm 2 , curing for 15 seconds.

[0083] Example 3

[0084] Preparation of modified silica particles

[0085] The hollow mesoporous silica particles are modified with hydroxyl groups to obtain hydroxyl-modified hollow mesoporous silica particles with a particle size of 100 nm.

[0086] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0087]

[0088] The particle size of the hydroxyl-modified hollow mesoporous silica particles is 100 nm.

[0089] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0090] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0091] S2, placing the mixture in a ring-shaped mold;

[0092] S3, UV curing the ring-shaped mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0093] UV curing conditions are as follows: irradiation intensity is 90mW / cm 2 , curing for 13 seconds.

[0094] Example 4

[0095] Preparation of modified silica particles

[0096] The dendritic silica particles were carboxyl-modified to obtain carboxyl-modified dendritic silica particles with a particle size of 80 nm.

[0097] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0098]

[0099] The particle size of the carboxyl-modified dendritic silica particles is 80 nm.

[0100] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0101] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0102] S2, placing the mixture in a bean curd-shaped mold;

[0103] S3, UV-curing the bean-shell-shaped mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0104] UV curing conditions are as follows: irradiation intensity is 100mW / cm 2 , cure for 10 seconds.

[0105] Example 5

[0106] Preparation of modified silica particles

[0107] The linear silica particles were amino-modified to obtain amino-modified linear silica particles with a particle size of 30 nm.

[0108] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0109]

[0110] The particle size of the amino-modified linear silica particles is 30 nm.

[0111] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0112] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0113] S2, placing the mixture in a rectangular mold;

[0114] S3, UV-curing the rectangular mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0115] UV curing conditions are as follows: irradiation intensity is 110mW / cm 2 , curing for 8s.

[0116] Example 6

[0117] Preparation of modified silica particles

[0118] The solid silica particles are carboxyl-modified to obtain carboxyl-modified solid silica particles having a particle size of 5 μm.

[0119] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0120]

[0121] The particle size of the carboxyl-modified silica particles is 5 μm.

[0122] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0123] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0124] S2, placing the mixture in a ring-shaped mold;

[0125] S3, UV curing the ring-shaped mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0126] UV curing conditions are as follows: irradiation intensity is 120mW / cm 2 , cure for 5s.

[0127] Comparative Example 1

[0128] Preparation of modified silica particles

[0129] The solid silica particles are amino-modified to obtain amino-modified solid silica particles with a particle size of 20 nm.

[0130] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0131]

[0132] The particle size of the amino-modified solid silica particles is 20 nm.

[0133] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0134] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0135] S2, placing the mixture in a ring-shaped mold;

[0136] S3, UV curing the ring-shaped mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0137] UV curing conditions are as follows: irradiation intensity is 70mW / cm 2 , curing for 20 seconds.

[0138] Comparative Example 2

[0139] Preparation of modified silica particles

[0140] The solid silica particles are amino-modified to obtain amino-modified solid silica particles with a particle size of 20 nm.

[0141] A light-cured isolation molding sheet for oral cavity with adjustable hardness and softness is made of the following raw material components by weight:

[0142]

[0143] The particle size of the amino-modified solid silica particles is 20 nm.

[0144] The steps for preparing the above-mentioned light-cured isolation molding sheet for oral use with adjustable hardness and softness are as follows:

[0145] S1, mixing the raw material components according to a ratio to obtain a mixture;

[0146] S2, placing the mixture in a ring-shaped mold;

[0147] S3, UV curing the ring-shaped mold to obtain an oral light-cured isolation molding sheet with adjustable hardness and softness;

[0148] UV curing conditions are as follows: irradiation intensity is 70mW / cm 2 , curing for 20 seconds.

[0149] The performance data of Examples 1-6 of the present invention and Comparative Examples 1-2 are shown in Table 2.

[0150] Table 2

[0151]

[0152] Compared with Example 1, Comparative Example 1 has no relevant test results because the polymethyl acrylate content is too low and exceeds the protection scope of the present invention, resulting in the inability to cure (3-mercaptopropyl)trimethoxysilane.

[0153] Compared with Example 1, Comparative Example 2 has too much 20 nm amino-modified solid silica particles, and the sample is brittle after curing and cannot be used, so there is no relevant test result for Comparative Example 2.

Claims

1. A light-cured isolation molding sheet for oral use with adjustable hardness and softness, comprising the following raw material components by weight: 64-85 parts of organosilane containing mercapto group; 5-30 parts of acrylic monomer; 5-10 parts of photoinitiator; 1-10 parts of modified silicon dioxide particles.

2. The photocurable isolation molding sheet according to claim 1, characterized in that: The mercapto-containing organic silane includes one or more of (3-mercaptopropyl)trimethoxysilane, 3-mercaptopropyl(dimethoxy)silane, and (3-mercaptopropyl)triethoxysilane.

3. The photocurable isolation molding sheet according to claim 1, characterized in that: The acrylic monomer includes one or more of methyl (meth)acrylate, ethyl (meth)acrylate, hydroxypropyl (meth)acrylate, n-butyl acrylate, cyclohexyl methacrylate, diethylene glycol diacrylate, and 9-anthracenemethyl acrylate.

4. The photocurable isolation molding sheet according to claim 1, characterized in that: The photoinitiator includes one or more of monoketone and diketone; preferably, the diketone includes one or more of camphorquinone, benzil, furil, phenanthrenequinone, 1-phenyl-1,2-propanedione.

5. The photocurable isolation molding sheet according to claim 1, characterized in that: The modified silica particles include one or more of amino-modified, carboxyl-modified and hydroxyl-modified silica particles; preferably, the shape structure of the modified silica particles includes one or more of solid, mesoporous, hollow mesoporous, multi-level porous, dendritic, nanowire, etc.; more preferably, the particle size of the modified silica particles is 20nm-5μm.

6. The photocurable isolation molding sheet according to claim 1, characterized in that: The light curing method is: UV curing; preferably, the irradiation intensity of UV curing is 70-120mW / cm 2 ; More preferably, the irradiation time of UV curing is 5-20s.

7. The photocurable isolation molding sheet according to claim 1, characterized in that: The Shore hardness of the photocurable isolation molding sheet is 30A-80A, preferably 34A-80A, and more preferably 34A-78A; and / or the transparency of the photocurable isolation molding sheet is 60%-95%, preferably 63%-95%, and more preferably 63%-93%.

8. A method for preparing the soft and hard adjustable oral light-curing isolation molding sheet as claimed in claims 1 to 7, comprising the following steps: S1, mixing the raw material components according to a ratio to obtain a mixture; S2, placing the mixture in a mold; S3, light-curing the mold; An isolation molded sheet is obtained.

9. Use of the hard-and-soft adjustable oral light-curing isolation molding sheet as described in claims 1 to 7 or the hard-and-soft adjustable oral light-curing isolation molding sheet prepared by the preparation method as described in claim 8 in oral treatment, preferably, the use in oral treatment includes use in dental restoration and dental products.

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