Light-cured resin, preparation method and application

Abstract

The invention discloses light-cured resin, a preparation method and application, and belongs to the technical field of light-cured 3D printing. The light-cured resin provided by the invention comprises the urethane acrylate oligomer, the modified acrylate oligomer and the reactive diluent, and the urethane acrylate oligomer can improve the toughness and reaction speed of the light-cured resin and reduce the volume shrinkage of the light-cured resin, so that the light-cured resin has good light-cured effect. The modified acrylate oligomer can improve the durability of the light-cured resin, adjust the hardness and toughness and reduce the volume shrinkage of the light-cured resin, and the reactive diluent can improve the hardness and toughness of the light-cured resin; the polyurethane acrylate oligomer, the modified acrylate oligomer and the reactive diluent are compounded, and the dosage of each component is limited, so that each component fully plays a synergistic role, and the light-cured resin has low volume shrinkage and high hardness, and keeps high toughness and durability at the same time.

Description

Technical Field

[0001] This application relates to the technical field of photocuring 3D printing, and particularly relates to a photocuring resin, a preparation method and an application thereof. Background Art

[0002] Photocuring 3D printing is a method of using ultraviolet light to irradiate a photocuring resin to produce 3D products by layer-by-layer curing. As an important consumable for photocuring 3D printing, the performance of the photocuring resin directly affects the performance of the product. Different products have different performance requirements for the photocuring resin. For example, dental materials require the photocuring resin to have low volume shrinkage, high hardness while maintaining high toughness and durability. However, the photocuring resins in the related art cannot meet the above requirements at the same time. Therefore, it is necessary to provide a photocuring resin for dental materials that can meet the above requirements at the same time. Summary of the Invention

[0003] The embodiments of this application provide a photocuring resin, a preparation method and an application thereof. The photocuring resin has low shrinkage, high hardness while maintaining high toughness and durability, and can be applied to photocuring 3D printing dental materials. The technical solution is as follows:

[0004] On the one hand, a photocuring resin is provided. The photocuring resin comprises the following components in parts by mass:

[0005] 40 - 65 parts of polyurethane acrylate oligomer, 10 - 20 parts of modified acrylate oligomer, 25 - 40 parts of active diluent, 1 - 5 parts of photoinitiator, 0.1 - 0.5 parts of light stabilizer, 0.001 - 0.01 parts of dye.

[0006] In a possible implementation manner, the active diluent comprises 5 - 10 parts by mass of bisphenol A di(meth)acrylate and 20 - 30 parts by mass of monofunctional or bifunctional monomers.

[0007] In another possible implementation manner, the monofunctional or bifunctional monomer is selected from at least one of acryloylmorpholine, isobornyl acrylate, Sartomer SR420NS, Sartomer SR259NS, Changxing Chemical EM2104, Changxing Chemical EM2204, Changxing Chemical EM2251, Changxing Chemical EM328, Rahn Chemical Genomer*1122.

[0008] In another possible implementation manner, the modified acrylate oligomer is selected from at least one of Lucite Elvacite4026, Changxing Chemical 6530B, BlueArc L-6020, BlueArc L-6040, Runao Chemical FSP2902.

[0009] In another possible implementation, the polyurethane acrylate oligomer is a bifunctional polyurethane acrylate oligomer with a viscosity of 1000 - 80000 cps and a cured hardness range of 44D - 90D.

[0010] In another possible implementation, the polyurethane acrylate oligomer is selected from at least one of Songda SD8976, Runao Chemical FSP8091, Runao Chemical CN1964NS, Rahn Chemical Genomer*4247, and Rahn Chemical Genomer*4256.

[0011] In another possible implementation, the photoinitiator is selected from at least one of diphenyl(2,4,6 - trimethylbenzoyl)phosphine oxide, ethyl 2,4,6 - trimethylbenzoyl phenylphosphinate, 2,4,6 - trimethylbenzoyl - bis(p - tolyl)phosphine oxide, and phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide.

[0012] In another possible implementation, the light stabilizer is selected from at least one of Tinuvin 292, Tinuvin 770, and Omnistab326.

[0013] On the other hand, a method for preparing a photocurable resin is provided. The preparation method includes:

[0014] According to the mass parts of each component, add the reactive diluent and the dye into a material tank and perform ultrasonic dispersion for 20 - 30 min.

[0015] Continue to add the photoinitiator and disperse at a rotation speed of 600 r / min - 800 r / min for 30 - 60 min.

[0016] Continue to add the polyurethane acrylate oligomer, the modified acrylate oligomer, and the light stabilizer, and disperse at a rotation speed of 600 r / min - 800 r / min for 45 - 60 min. After filtration and static defoaming, the photocurable resin is obtained.

[0017] On the other hand, an application of the photocurable resin in photocurable 3D printing dental materials is provided.

[0018] An embodiment of the present application provides a photocurable resin, which includes a polyurethane acrylate oligomer, a modified acrylate oligomer, and an active diluent. Among them, the polyurethane acrylate oligomer can improve the toughness and reaction rate of the photocurable resin, reduce the volume shrinkage of the photocurable resin, the modified acrylate oligomer can improve the durability of the photocurable resin, adjust the hardness and toughness, and at the same time reduce the volume shrinkage of the photocurable resin, and the active diluent can improve the hardness and toughness of the photocurable resin; by compounding the polyurethane acrylate oligomer, the modified acrylate oligomer, and the active diluent and limiting the dosage of each component, the components can give full play to their synergistic effects, so that the photocurable resin has high toughness and durability while having a low volume shrinkage and high hardness. And, the photocurable resin also includes a light stabilizer and a dye. The light stabilizer can enhance the color stability of the photocurable resin during the post-curing process and under light aging conditions. The dye can not only provide the required color for the photocurable resin, but also reduce the yellowing effect of the photocurable resin.

[0019] It should be understood that the above general description and the following detailed description are only exemplary and do not limit the present disclosure. Detailed Description of the Invention

[0020] To make the technical solutions and advantages of the present application clearer, the embodiments of the present application will be further described in detail below.

[0021] On the one hand, an embodiment of the present application provides a photocurable resin, which includes the following components in parts by mass:

[0022] 40-65 parts of polyurethane acrylate oligomer, 10-20 parts of modified acrylate oligomer, 25-40 parts of active diluent, 1-5 parts of photoinitiator, 0.1-0.5 parts of light stabilizer, 0.001-0.01 parts of dye.

[0023] Among them, the mass fraction of the polyurethane acrylate oligomer can be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 53 parts, 55 parts, 58 parts, 60 parts, 63 parts, 65 parts, the mass fraction of the modified acrylate oligomer can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, the mass fraction of the photoinitiator can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, the mass fraction of the light stabilizer can be 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, and the mass fraction of the dye can be 0.001 part, 0.002 part, 0.003 part, 0.004 part, 0.005 part, 0.006 part, 0.007 part, 0.008 part, 0.009 part, 0.01 part.

[0024] An embodiment of the present application provides a photocurable resin, which includes a polyurethane acrylate oligomer, a modified acrylate oligomer, and an active diluent. Among them, the polyurethane acrylate oligomer can improve the toughness and reaction rate of the photocurable resin, reduce the volume shrinkage of the photocurable resin, the modified acrylate oligomer can improve the durability of the photocurable resin, adjust the hardness and toughness, and at the same time reduce the volume shrinkage of the photocurable resin, and the active diluent can improve the hardness and toughness of the photocurable resin; the polyurethane acrylate oligomer, the modified acrylate oligomer, and the active diluent are compounded, and the amounts of each component are limited, so that each component can give full play to the synergistic effect, so that the photocurable resin has high toughness and durability while having a low volume shrinkage and a high hardness. And, the photocurable resin also includes a light stabilizer and a dye. The light stabilizer can enhance the color stability of the photocurable resin during the post-curing process and under light aging conditions. The dye can not only provide the required color for the photocurable resin, but also reduce the yellowing effect of the photocurable resin.

[0025] In a possible implementation manner, the active diluent includes 5 to 10 parts by mass of bisphenol A di(meth)acrylate and 20 to 30 parts by mass of a monofunctional or bifunctional monomer.

[0026] Among them, the mass fraction of bisphenol A di(meth)acrylate can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, and the mass fraction of the monofunctional or bifunctional monomer can be 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts.

[0027] In a possible implementation manner, the bisphenol A di(meth)acrylate is selected from at least one of Changxing Chemical EM3260 (BPA2EODMA), Changxing Chemical EM3265 (BPA10EODMA), Changxing Chemical EM3262 (BPA2.6EODMA), Changxing Chemical EM3261-8 (BPA4EODMA), Changxing Chemical EM2261, Changxing Chemical EM2265, Changxing Chemical EM2266, Sartomer SR348NS, Sartomer SR601NS.

[0028] In a possible implementation manner, the monofunctional or bifunctional monomer is selected from at least one of acryloylmorpholine (ACMO), isobornyl acrylate (IBOA), Sartomer SR420NS (TMCHA), Sartomer SR259NS (polyethylene glycol (200) diacrylate), Changxing Chemical EM2104 (TMCHA), Changxing Chemical EM2204 (DCPDA), Changxing Chemical EM2251 (NPG2PDOA), Changxing Chemical EM328 (TEGDMA), Rahn Chemical Genomer*1122.

[0029] Among them, ACMO, IBOA, Sartomer SR420NS, Changxing Chemical EM2104, Sartomer SR420NS, and Rahn Chemical Genomer*1122 are monofunctional monomers, and Sartomer SR259NS, Changxing Chemical EM2204, EM2251, and EM328 are difunctional monomers.

[0030] In the embodiments of the present application, bisphenol A di(meth)acrylate is a type of monomer containing bisphenol A and ethoxylated to varying degrees. Due to its bisphenol A structure, this type of monomer has the characteristics of high reactivity, fast reaction rate, high hardness, low skin irritation, good heat resistance, low odor, and low volatility. The functionality of the monomer directly affects the viscosity, curing speed, curing degree, and toughness of the photocurable resin. Monomers with high functionality can provide more reaction sites, thereby accelerating the curing process, increasing the crosslinking density, and further improving the hardness and strength of the photocurable resin. However, monomers with high functionality, due to the excessive crosslinking density, will cause the photocurable resin to become hard, reduce the elongation at break, and be prone to fracture. At the same time, monomers with high functionality usually have poor dilution ability, resulting in a higher viscosity and poorer fluidity of the system. Therefore, in the present application, monofunctional or difunctional monomers are used, and the monofunctional or difunctional monomers are compounded with bisphenol A di(meth)acrylate as an active diluent, and then compounded with other components, which can not only make the photocurable resin have a suitable viscosity, but also effectively improve the hardness and toughness of the photocurable resin.

[0031] In one possible implementation, the modified acrylate oligomer is selected from at least one of Lucite Elvacite 4026, Changxing Chemical 6530B, Blue Color Road L-6020, Blue Color Road L-6040, and Runao Chemical FSP2902.

[0032] In this implementation, these modified acrylate oligomers such as Lucite Elvacite 4026, Changxing Chemical 6530B, Blue Color Road L-6020, Blue Color Road L-6040, and Runao Chemical FSP2902 are all acrylate oligomers modified with UV-reactive functional groups. When in use, if the viscosity of the above-mentioned modified acrylate oligomer is within the range of 10,000 - 30,000 cps, no dilution is required. If the viscosity is too high and exceeds the above range, active diluents such as 4-acryloylmorpholine (ACMO), 3,3,5-trimethylcyclohexyl acrylate (TMCHA), 1,6-hexanediol diacrylate (HDDA), etc. can be used to pre-dilute the above-mentioned modified acrylate oligomer to a viscosity of 10,000 - 30,000 cps.

[0033] It should be noted that the reactive diluent here is the reactive diluent used to dilute the viscosity of the modified acrylate oligomer in advance before preparing the photocurable resin, rather than the reactive diluent in the formulation composition.

[0034] Conventional acrylate resins have advantages such as high flexibility, water resistance, yellowing resistance, and good tear resistance, but they do not have reactive functional groups and have extremely high viscosities, making it difficult to apply them in photocurable 3D printing. In this application, a special acrylate modified with UV reactive functional groups is used. By modifying the acrylate main chain, photoinitiating activity is introduced, and at the same time, the viscosity in use is reduced through monomer pre-dissolution, enabling it to be applied in photocurable 3D printing.

[0035] In this application, the modified acrylate oligomer within the above viscosity range is compounded with other components, which can not only make the photocurable resin have appropriate viscosity and curing speed, but also make the photocurable resin have high hardness, flexibility, durability, and low volume shrinkage.

[0036] In a possible implementation manner, the polyurethane acrylate oligomer is selected from at least one of Songda SD8976, Runao Chemical FSP8091, Runao Chemical CN1964NS, Rahn Chemical Genomer*4247, and Rahn Chemical Genomer*4256.

[0037] In this implementation manner, the above polyurethane acrylate oligomers are all bifunctional polyurethane acrylate oligomers, with a normal temperature viscosity of 1000 - 80000 cps and a cured hardness range of 44D - 90D. Among them, Rahn Chemical Genomer*4247 and Genomer*4256 are aliphatic polyurethane methacrylates.

[0038] The viscosity, functionality, and hardness of the polyurethane acrylate oligomer directly affect the performance of the photocurable resin. If the hardness is too high, the elongation and toughness are usually poor; if the hardness is too low, the shape retention is poor, both of which will limit its application. The hardness of the polyurethane acrylate oligomer within the above hardness range is relatively moderate, and after adjusting by adding other components, it can meet the usage requirements. The viscosity and functionality of the polyurethane acrylate oligomer will also affect the curing speed and other properties of the photocurable resin. For example, the level of functionality determines the length and crosslinking density of the polymer molecular chain, thereby affecting the mechanical properties of the photocurable resin. At the same time, the level of functionality will also affect the tensile strength, tensile elastic modulus, elongation at break and other properties of the photocurable resin, thus affecting the durability of the photocurable resin. If the resin viscosity is too high, a large amount of reactive diluent needs to be added for dilution, which will lead to a reduction in mechanical properties and a relatively high volume shrinkage.

[0039] In this application, a bifunctional polyurethane acrylate oligomer within the above-mentioned cured hardness and viscosity ranges is compounded with other components, which can not only endow the photocurable resin with an appropriate curing rate, but also enable the photocurable resin to have high hardness, flexibility, durability and low volume shrinkage.

[0040] In a possible implementation, the photoinitiator is selected from at least one of diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator TPO), ethyl 2,4,6-trimethylbenzoyl phenylphosphinate (photoinitiator TPO-L), 2,4,6-trimethylbenzoyl-bis(p-tolyl)phosphine oxide (photoinitiator TMO), and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819).

[0041] Under the irradiation of ultraviolet or visible light, the photoinitiator can generate free radicals to initiate the polymerization reaction of double bonds.

[0042] In a possible implementation, the light stabilizer is selected from at least one of Tinuvin 292, Tinuvin 770, and Omnistab326.

[0043] In the embodiments of this application, the above-mentioned light stabilizer can enhance the color stability of the photocurable resin during the post-curing process and under light aging conditions.

[0044] In a possible implementation, the dye is selected from blue dyes, such as at least one of cryptocrystalline violet, ultramarine, and blue dye.

[0045] In the embodiments of this application, using the above-mentioned dye can not only provide the required color for the photocurable resin, but also effectively reduce the yellowing effect of the photocurable resin.

[0046] On the other hand, the embodiments of this application provide a preparation method of a photocurable resin, and the preparation method includes:

[0047] Step 1: Add the reactive diluent and the dye to the material tank according to the mass parts of each component, and perform ultrasonic dispersion.

[0048] Add bisphenol A di(meth)acrylate, monofunctional or bifunctional monomer and the dye to the material tank, perform ultrasonic dispersion for 20 - 30 min, and proceed to the next step after dissolution.

[0049] Among them, the ultrasonic dispersion time can be 20 min, 21 min, 22 min, 23 min, 24 min, 25 min, 26 min, 27 min, 28 min, 29 min, or 30 min.

[0050] Step 2: Continuously add a photoinitiator and disperse it at a speed of 600 r / min to 800 r / min for 30 to 60 minutes.

[0051] Continuously add a photoinitiator to the feed tank and disperse it at a speed of 600 r / min to 800 r / min for 30 to 60 minutes using a high-speed disperser.

[0052] Among them, the rotational speed can be 600 r / min, 650 r / min, 680 r / min, 700 r / min, 750 r / min, 780 r / min, 800 r / min, and the dispersion time can be 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min.

[0053] Step 3: Continuously add a polyurethane acrylate oligomer, a modified acrylate oligomer, and a light stabilizer, disperse it at a speed of 600 r / min to 800 r / min for 45 to 60 minutes, filter, and let it stand to defoam to obtain a photocurable resin.

[0054] The rotational speed in this step can be 600 r / min, 650 r / min, 680 r / min, 700 r / min, 750 r / min, 780 r / min, 800 r / min, and the dispersion time can be 45 min, 48 min, 50 min, 52 min, 55 min, 56 min, 58 min, 60 min.

[0055] The photocurable resin prepared in this application is compounded with a polyurethane acrylate oligomer, a modified acrylate oligomer, and an active diluent, and the dosages of each component are limited. Each component gives full play to its synergistic effect, so that the photocurable resin has low volume shrinkage and high hardness while maintaining high toughness and durability. In addition, the photocurable resin also includes a light stabilizer and a dye. The light stabilizer can enhance the color stability of the photocurable resin during the post-curing process and under light aging conditions. The dye can not only provide the required color for the photocurable resin but also reduce the yellowing effect of the photocurable resin.

[0056] On the other hand, this application also provides an application of a photocurable resin in a photocurable 3D printing dental material.

[0057] Among them, the dental material can be an orthodontic dental material or other dental materials, and no specific limitation is made thereto.

[0058] To make the technical solutions and advantages of this application clearer, the following will be elaborated in detail through specific examples.

[0059] In the following specific embodiments, operations not specified with conditions are carried out under conventional conditions or conditions recommended by the manufacturer. Raw materials not specified with manufacturers and specifications are all conventional products that can be obtained through commercial purchase.

[0060] Among them, the polyurethane acrylate oligomer is selected from Songda SD8976, Runao Chemical FSP8091, Rahn Chemical Genomer*4247, Runao Chemical CN1964NS;

[0061] The modified acrylate oligomer is selected from Runao Chemical FSP2902;

[0062] Bisphenol A di(meth)acrylate is selected from Changxing Chemical EM3261-8;

[0063] The monofunctional or bifunctional monomer is selected from ACMO, Changxing Chemical EM2104, EM2251;

[0064] The photoinitiator is selected from TPO, TMO, TPO-L;

[0065] The light stabilizer is selected from Tinuvin 292;

[0066] The dye is selected from ultramarine.

[0067] Example 1

[0068] Example 1 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of ACMO, 5 parts by mass of EM3261-8 and 0.004 parts by mass of ultramarine into a material tank, and disperse ultrasonically; then continue to add 3 parts by mass of the photoinitiator TPO and disperse evenly; then continue to add 53 parts by mass of CN1964NS, 20 parts by mass of FSP2902 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter and stand for defoaming to obtain the photocurable resin.

[0069] Example 2

[0070] Example 2 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8 and 0.004 parts by mass of ultramarine into a material tank, and disperse ultrasonically; then continue to add 3 parts by mass of the photoinitiator TPO and disperse evenly; then continue to add 63 parts by mass of FSP8091, 10 parts by mass of FSP2902 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter and stand for defoaming to obtain the photocurable resin.

[0071] Example 3

[0072] Example 3 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of ACMO, 5 parts by mass of EM3261-8 and 0.004 parts by mass of ultramarine into a feed tank, and disperse them by ultrasonic; Continuously add 3 parts by mass of photoinitiator TPO and disperse evenly; Continuously add 53 parts by mass of FSP8091, 20 parts by mass of FSP2902 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and stand for defoaming to obtain the photocurable resin.

[0073] Example 4

[0074] Example 4 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8 and 0.004 parts by mass of ultramarine into a feed tank, and disperse them by ultrasonic; Continuously add 3 parts by mass of photoinitiator TMO and disperse evenly; Continuously add 48 parts by mass of SD8976, 15 parts by mass of FSP2902 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and stand for defoaming to obtain the photocurable resin.

[0075] Example 5

[0076] Example 5 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8 and 0.004 parts by mass of ultramarine into a feed tank, and disperse them by ultrasonic; Continuously add 3 parts by mass of photoinitiator TMO and disperse evenly; Continuously add 53 parts by mass of SD8976, 10 parts by mass of FSP2902 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and stand for defoaming to obtain the photocurable resin.

[0077] Example 6

[0078] Example 6 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2251, 5 parts by mass of EM3261-8 and 0.004 parts by mass of ultramarine into a feed tank, and disperse them by ultrasonic; Continuously add 3 parts by mass of TPO-L and disperse evenly; Continuously add 53 parts by mass of Genomer*4247, 10 parts by mass of FSP2902 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and stand for defoaming to obtain the photocurable resin.

[0079] Example 7

[0080] Example 7 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a storage tank, and disperse them by ultrasonic wave; continue to add 3 parts by mass of photoinitiator TMO, and disperse evenly; continue to add 30 parts by mass of SD8976, 33 parts by mass of FSP8091, 10 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, and disperse evenly. After filtration and standing for defoaming, the photocurable resin is obtained.

[0081] Comparative Example 1

[0082] Comparative Example 1 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of ACMO, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a storage tank, and disperse them by ultrasonic wave; continue to add 3 parts by mass of photoinitiator TPO, and disperse evenly; continue to add 53 parts by mass of Genomer*4247, 20 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, and disperse evenly. After filtration and standing for defoaming, the photocurable resin is obtained.

[0083] Comparative Example 2

[0084] Comparative Example 2 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of ACMO, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a storage tank, and disperse them by ultrasonic wave; continue to add 3 parts by mass of photoinitiator TPO, and disperse evenly; continue to add 63 parts by mass of FSP8091, 10 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, and disperse evenly. After filtration and standing for defoaming, the photocurable resin is obtained.

[0085] Comparative Example 3

[0086] Comparative Example 3 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a storage tank, and disperse them by ultrasonic wave; continue to add 3 parts by mass of photoinitiator TMO, and disperse evenly; continue to add 58 parts by mass of SD8976, 5 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, and disperse evenly. After filtration and standing for defoaming, the photocurable resin is obtained.

[0087] Comparative Example 4

[0088] Comparative Example 4 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a material tank, and disperse them by ultrasonic; Then continue to add 3 parts by mass of photoinitiator TPO and disperse evenly; Then continue to add 53 parts by mass of SD8976, 10 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and let stand to defoam to obtain the photocurable resin.

[0089] Comparative Example 5

[0090] Comparative Example 5 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a material tank, and disperse them by ultrasonic; Then continue to add 3 parts by mass of TMO and disperse evenly; Then continue to add 40 parts by mass of SD8976, 23 parts by mass of FSP8091, 10 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and let stand to defoam to obtain the photocurable resin.

[0091] Comparative Example 6

[0092] Comparative Example 6 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a material tank, and disperse them by ultrasonic; Then continue to add 3 parts by mass of TMO and disperse evenly; Then continue to add 20 parts by mass of SD8976, 43 parts by mass of FSP8091, 10 parts by mass of FSP2902, and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and let stand to defoam to obtain the photocurable resin.

[0093] Comparative Example 7

[0094] Comparative Example 7 provides a photocurable resin, which is prepared by the following method: Add 22 parts by mass of EM2104, 5 parts by mass of EM3261-8, and 0.004 parts by mass of ultramarine blue into a material tank, and disperse them by ultrasonic; Then continue to add 3 parts by mass of TMO and disperse evenly; Then continue to add 63 parts by mass of SD8976 and 0.4 parts by mass of Tinuvin 292, disperse evenly, filter, and let stand to defoam to obtain the photocurable resin.

[0095] The formulations of Examples 1 to 7 above can be seen in Table 1 below, and the formulations of Comparative Examples 1 to 7 can be seen in Table 2 below.

[0096] Table 1

[0097]

[0098]

[0099] Table 2

[0100]

[0101] Application examples

[0102] The photocurable resins prepared in Examples 1-7 and Comparative Examples 1-7 were 3D printed using a DLP type 3D printer with a wavelength of 405 nm and a printer light intensity of 1-5 mW·cm -1 , and the printing thickness of each layer was set to 100 μm, and the printing time for a single layer was 5-10 s.

[0103] Test method: The appearance of the printed product was judged by visual inspection. If there was no obvious yellowing and the details were clear, it was considered qualified; the mechanical property modulus and tensile elongation were tested using a tensile testing machine, and the size of the specimen spline was about 15 mm wide and 120 μm thick; the degree of curing was tested using an infrared spectrometer. After the printed sample was cut with a knife, the cross-section was selected for infrared spectrum scanning; the degree of curing was obtained by calculating the ratio of the double bond rate in the liquid state to the double bond rate of the cured film; the number of bending times of the printed sample was tested using a mechanical reciprocating structure to test the durability of the sample when it was bent and broken. The test results are shown in Table 3 below.

[0104] Table 3

[0105]

[0106] Comparing Example 1, Example 3 and Comparative Example 1, the difference lies in the different polyurethane acrylate oligomers, which is used to consider the influence of resins with different properties on the properties of the printed samples. It can be seen from Table 3 that there are great differences in the properties of the printed samples corresponding to Example 1, Example 3 and Comparative Example 1, especially in terms of mechanical property modulus, number of bending times and tensile elongation.

[0107] Comparing Example 2 and Comparative Example 2, the difference lies in the different monomers. It can be seen from Table 3 that when the monomer ACMO is used, the curing rate of the sample is faster and the degree of curing is higher.

[0108] Comparing Example 4, Example 5 and Comparative Example 3, the difference lies in the different compounding ratios of polyurethane acrylate oligomer (SD8976) and modified acrylate oligomer (FSP2902). It can be seen from Table 3 that when the compounding ratios of polyurethane acrylate oligomer (SD8976) and modified acrylate oligomer (FSP2902) are different, there are great differences in the mechanical property modulus, tensile elongation and hardness of the samples. In particular, the amount of modified acrylate oligomer (FSP2902) will affect the overall hardness and tensile elongation of the system.

[0109] Comparing Example 5, Example 6 with Comparative Example 4, the difference lies in the photoinitiator. The photoinitiator used in Example 5 is TMO, the photoinitiator used in Example 6 is TPO-L, and the photoinitiator used in Comparative Example 4 is TPO. It can be seen from Table 3 that the sample corresponding to Example 5 has a higher curing degree. Thus, it can be shown that when the photoinitiator is TMO, compared with TPO and TPO-L, the sample has a higher curing degree.

[0110] Comparing Example 7 with Comparative Example 5 and Comparative Example 6, the difference lies in that the photoinitiator TMO is used, and when other components remain unchanged, SD8976 and FSP8091 are compounded as the polyurethane acrylate oligomer, and the differences in the mechanical properties, curing degree and bending times of the samples under different compounding ratios are compared. It can be seen that when SD8976 and FSP8091 with different ratios are compounded as the polyurethane acrylate oligomer, it has a certain degree of influence on the mechanical properties, curing degree and bending times of the samples.

[0111] Comparing Example 5 with Comparative Example 7, the difference is that Comparative Example 7 only uses the polyurethane acrylate oligomer and does not add the modified acrylate oligomer. It can be seen from Table 3 that compared with Comparative Example 7, after adding the modified acrylate oligomer in Example 5, although the modulus and hardness of the sample decrease, the elongation at break and bending resistance performance are greatly improved. Thus, it can be shown that the addition of the modified acrylate oligomer is beneficial to improving the flexibility and durability of the sample.

[0112] In summary, by adjusting the polyurethane acrylate oligomer, modified acrylate oligomer, active diluent and initiator, the mechanical properties such as the mechanical modulus and tensile elongation at break of the sample can be improved simultaneously, further meeting the application of dental materials. Due to the reproductive toxicity problem of the photoinitiator TPO, it is included in the EU Reach list and there are restrictions on its application. Therefore, the bottom surface curing degree test of TMO is introduced, and the selection of different photoinitiators is compared, indicating that the curing degree of the sample corresponding to the photoinitiator TMO in the same amount is higher than that of traditional photoinitiators such as TPO and TPO-L.

[0113] The above description is only for the convenience of those skilled in the art to understand the technical solution of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A photocurable resin, characterized in that, The photocurable resin comprises the following components in parts by mass: 40 - 65 parts of polyurethane acrylate oligomer, 10 - 20 parts of modified acrylate oligomer, 25 - 40 parts of reactive diluent, 1 - 5 parts of photoinitiator, 0.1 - 0.5 parts of light stabilizer, 0.001 - 0.01 parts of dye.

2. The photocurable resin according to claim 1, wherein, The reactive diluent comprises 5 - 10 parts by mass of bisphenol A di(meth)acrylate and 20 - 30 parts by mass of monofunctional or difunctional monomer.

3. The photocurable resin according to claim 2, wherein, The bisphenol A di(meth)acrylate is selected from at least one of Changxing Chemical EM3260, Changxing Chemical EM3265, Changxing Chemical EM3262, Changxing Chemical EM3261 - 8, Changxing Chemical EM2261, Changxing Chemical EM2265, Changxing Chemical EM2266, Sartomer SR348NS, Sartomer SR601NS.

4. The photocurable resin according to claim 2, wherein The monofunctional or difunctional monomer is selected from at least one of acryloylmorpholine, isobornyl acrylate, Sartomer SR420NS, Sartomer SR259NS, Changxing Chemical EM2104, Changxing Chemical EM2204, Changxing Chemical EM2251, Changxing Chemical EM328, Rahn Chemical Genomer*1122.

5. The photocurable resin according to claim 1, wherein The modified acrylate oligomer is selected from at least one of Lucite Elvacite 4026, Changxing Chemical 6530B, Blue Color Road L - 6020, Blue Color Road L - 6040, Runao Chemical FSP2902.

6. The photocurable resin according to claim 1, wherein The polyurethane acrylate oligomer is a difunctional polyurethane acrylate oligomer, with a viscosity of 1000 - 80000 cps and a cured hardness range of 44D - 90D.

7. The photocurable resin according to claim 6, wherein The polyurethane acrylate oligomer is selected from at least one of Songda SD8976, Runao Chemical FSP8091, Runao Chemical CN1964NS, Rahn Chemical Genomer*4247, Rahn Chemical Genomer*4256.

8. The photocurable resin according to claim 1, wherein The photoinitiator is selected from at least one of diphenyl(2,4,6 - trimethylbenzoyl)phosphine oxide, ethyl 2,4,6 - trimethylbenzoyl phenylphosphonate, 2,4,6 - trimethylbenzoyl - bis(p - tolyl)phosphine oxide, phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide.

9. A method for preparing the photocurable resin according to any one of claims 1 to 8, characterized in that, The preparation method comprises: Adding the reactive diluent and the dye into a feed tank according to the parts by mass of each component, and performing ultrasonic dispersion for 20 - 30 min; Continuously adding the photoinitiator, and dispersing at a rotation speed of 600 r / min - 800 r / min for 30 - 60 min; Continuously adding the polyurethane acrylate oligomer, the modified acrylate oligomer and the light stabilizer, and dispersing at a rotation speed of 600 r / min - 800 r / min for 45 - 60 min. After filtration and static defoaming, the photocurable resin is obtained.

10. Use of the photocurable resin according to any one of claims 1 - 8 in photocurable 3D printing dental materials.

Images