Photosensitive resin composition, method of use and applications thereof

Abstract

The present disclosure relates to a photosensitive resin composition, a use method and an application thereof. The raw materials of the photosensitive resin composition include the following components: 55-75 parts by weight of polyurethane acrylate oligomer; 5-25 parts by weight of monofunctional acrylate monomer; 5-15 parts by weight of multifunctional acrylate monomer; and 1-5 parts by weight of initiator. The photosensitive resin composition provided by the present disclosure has low viscosity and fast curing speed, is suitable for light curing 3D printing technology, and has good toughness and low water absorption after curing and forming. The denture base prepared has no water absorption, good toughness, stable performance and strong impact resistance.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of materials, in particular to a photosensitive resin composition, a use method and applications thereof. BACKGROUND

[0002] A complete denture is composed of two parts, namely artificial teeth and denture base. The denture base covers the alveolar ridge of the missing teeth, serves as the base for arranging artificial teeth, can connect the parts of the denture into a whole, and evenly transmit the force borne by the artificial teeth to the oral tissue. The denture base can be divided into resin base and metal base according to the material, and the resin base is currently commonly used.

[0003] Traditional denture base resin includes heat-curing denture base resin and self-curing denture base resin. The heat-curing denture base resin includes a liquid agent and a powder agent, the liquid agent is composed of methyl methacrylate, a crosslinking agent, a polymerization inhibitor and a UV light absorber, and the powder agent is composed of polymethyl methacrylate homopolymer powder or copolymer powder and pigments. When used, a separating agent is coated on a mold box, then the liquid agent and the powder agent are mixed to a certain coagulation state, and then the mixed liquid agent and the powder agent are filled into the mold box and heated to form. The self-curing denture base resin also includes a liquid agent and a powder agent, the liquid agent is composed of methyl methacrylate, a small amount of accelerator, a polymerization inhibitor and a UV light absorber, and the powder agent is composed of polymethyl methacrylate homopolymer powder or copolymer powder, a small amount of initiator and colorant. When used, it is similar to the heat-curing denture base resin, only without the heating process, and can be cured and formed at room temperature.

[0004] However, the traditional denture base resin has a complex process, multiple steps, a long cycle and is very inconvenient to use when preparing a denture base. The light-curing 3D printing technology has high precision, fast printing speed and simple process, and has been widely used in the field of oral medicine. If the light-curing 3D printing technology is used to replace the traditional denture base preparation process, the production time can be effectively shortened, the cost can be reduced, the labor input can be reduced, and the production efficiency can be improved. At the same time, the substantial reduction in the manufacturing cycle can reduce the number of visits of patients before receiving denture repair treatment to a certain extent, and reduces the time and treatment cost of patients.

[0005] The liquid photosensitive resin matched with the light-curing 3D printing technology requires low viscosity and fast curing speed. However, the traditional denture base resin contains a large amount of polymethyl methacrylate with a large molecular weight, resulting in a large viscosity of the resin system, which cannot be applied to light curing. In addition, the photosensitive resin for light-curing 3D printing on the market has the defects of poor water absorption or poor toughness, and therefore cannot be used in denture bases.

[0006] Therefore, it is particularly important to develop a photosensitive resin suitable for light-curing 3D printing technology, having low water absorption and high toughness, and capable of being applied to denture bases. SUMMARY

[0007] To solve the above technical problems, the present disclosure provides a photosensitive resin composition, a use method and an application thereof.

[0008] In a first aspect, the present disclosure provides a photosensitive resin composition, raw materials including the following components in mass percentage:

[0009]

[0010] The present disclosure provides strength and partial toughness by using polyurethane acrylate oligomers in the main part of the formula, multifunctional acrylate monomers act as crosslinking agents, monofunctional acrylate monomers further reduce the viscosity of the system and maintain the strength, the three are compatible and cooperate with other components, and develop a 3D printing photosensitive resin suitable for photocuring, which has fast curing speed, good toughness after curing, low water absorption and strong impact resistance, and can be applied to 3D printing of denture bases.

[0011] In the present disclosure, the content of the polyurethane acrylate oligomer can be 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, etc.

[0012] In the present disclosure, the content of the monofunctional acrylate monomer can be 8 parts by weight, 12 parts by weight, 16 parts by weight, 20 parts by weight, 24 parts by weight, etc.

[0013] In the present disclosure, the content of the multifunctional acrylate monomer can be 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, etc.

[0014] In the present disclosure, the content of the initiator can be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, etc.

[0015] As a preferred technical solution of the present disclosure, the raw materials of the photosensitive resin composition further include 0.01-10 parts by weight of hyperbranched oligomers, such as 1 part by weight, 2 parts by weight, 5 parts by weight, 8 parts by weight, etc.

[0016] The present disclosure can further improve the poor water absorption and toughness of the resin after curing by introducing hyperbranched oligomers, and the prepared denture base has good toughness and strong impact resistance, and will not be damaged during daily use.

[0017] As a preferred technical solution of the present disclosure, the hyperbranched oligomer is selected from hyperbranched acrylates with functionality of 6-30 and viscosity of 1500-30000 cps, and the viscosity is the viscosity at 25°C.

[0018] The functionality described in the present disclosure is the average functionality, and the 6-30 can be 7, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, etc.

[0019] The viscosity is 1500-30000 cps, which can be 3000 cps, 5000 cps, 10000 cps, 20000 cps, etc.

[0020] As a preferred technical solution of the present disclosure, the polyurethane acrylate oligomer is selected from polyurethane (meth) acrylate and / or polyester polyurethane (meth) acrylate.

[0021] The polyurethane (meth) acrylate oligomer described in the present disclosure can be a polyurethane methacrylate oligomer, or a polyurethane acrylate. The same understanding applies to other "(meth)".

[0022] The polyurethane (meth) acrylate oligomer described in the present disclosure is a non-polar, hydrophobic polyurethane (meth) acrylate oligomer, which provides strength and partial toughness, while cooperating with multi-functional monomers and single-functional monomers. After curing and forming, the toughness is better, the impact resistance is strong, it is hydrophobic, and it is not easy to have problems such as performance degradation or volume expansion due to water absorption.

[0023] As a preferred technical solution of the present disclosure, the molecular weight of the polyurethane (meth) acrylate is 500-7000, such as 600, 800, 1000, 2000, 5000, etc.

[0024] As a preferred technical solution of the present disclosure, the molecular weight of the polyester polyurethane (meth) acrylate is 2000-10000, such as 3000, 4000, 5000, 6000, 8000, etc.

[0025] In the present disclosure, the molecular weight refers to the average molecular weight.

[0026] As a preferred technical solution of the present disclosure, the single-functional acrylate monomer is selected from a fatty cyclic single-functional acrylate monomer.

[0027] As a preferred technical solution of the present disclosure, the single-functional acrylate monomer is selected from any one or a combination of at least two of isobornyl (meth) acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, and 4-tert-butylcyclohexyl acrylate.

[0028] The present disclosure introduces an aliphatic monofunctional acrylate monomer containing a fatty ring, which can further improve the strength of the resin, while the monofunctional group can reduce the overall functionality and crosslinking density of the system, thereby reducing the brittleness and viscosity of the resin and improving the toughness.

[0029] As a preferred technical solution of the present disclosure, the multifunctional acrylate monomer is selected from any one or a combination of at least two of the following: difunctional or trifunctional acrylate monomers without benzene ring, preferably 1,6-hexanediol di(meth)acrylate, tripropylene glycol diacrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, dodecyl dimethyl acrylate, tricyclodecane dimethanol diacrylate.

[0030] The present disclosure introduces a difunctional or trifunctional acrylate monomer without benzene ring as a crosslinking agent, which does not increase the brittleness of the resin compared to aromatic structures, and when used with aliphatic monofunctional acrylate monomers that can reduce the functionality, a photosensitive resin composition with good toughness can be obtained.

[0031] As a preferred technical solution of the present disclosure, the initiator is selected from 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate (TPO-L) and / or phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (819).

[0032] Since the photosensitive resin composition prepared by the present disclosure is applied to denture bases, it is used at the entrance, so the initiator is preferably selected from non-toxic initiators.

[0033] As a preferred technical solution of the present disclosure, the raw materials of the photosensitive resin composition further include 0.005-0.02 parts by weight of an ultraviolet light absorber, such as 0.008 parts by weight, 0.01 parts by weight, 0.015 parts by weight, 0.018 parts by weight, etc.

[0034] As a preferred technical solution of the present disclosure, the ultraviolet light absorber is selected from ultraviolet light absorber UV-1164, ultraviolet light absorber UV-P, ultraviolet light absorber UV-1990, or ultraviolet light absorber UV-4990.

[0035] As a preferred technical solution of the present disclosure, the raw materials of the photosensitive resin composition further include 0.05-0.2 parts by weight of a light stabilizer, such as 0.08 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.18 parts by weight, etc.

[0036] As a preferred technical solution of the present disclosure, the light stabilizer is selected from light stabilizer LS-144, hindered amine light stabilizer HS-508 (292), or light stabilizer 770.

[0037] As a preferred technical solution of the present disclosure, the viscosity of the photosensitive resin composition is 500-1200 cps, when the viscosity of the composition provided by the present disclosure is within this range, the requirements of 3D printing can be well met.

[0038] As a preferred technical solution of the present disclosure, the raw materials of the photosensitive resin composition include the following components in mass percentage:

[0039]

[0040] In the present disclosure, the sum of the amount of the polyurethane acrylate oligomer, the monofunctional acrylate monomer, the multifunctional acrylate monomer, the initiator and the hyperbranched oligomer is preferably 100 parts by weight.

[0041] In a second aspect, the present disclosure provides an application of the photosensitive resin composition of the first aspect in the preparation of a denture or a denture base.

[0042] The photosensitive resin composition provided by the present disclosure has low water absorption and good toughness, and can be applied to a denture or a denture base. When worn by a user, the performance will not decrease or the volume will not expand to cause discomfort due to water absorption, and the denture base is also not easy to break.

[0043] In a third aspect, the present disclosure provides a use method of the photosensitive resin composition of the first aspect, including the following steps: mixing the components in a formula amount, and performing light curing.

[0044] The photosensitive resin composition provided by the present disclosure has low viscosity and fast curing speed, and the target product such as a denture or a denture base can be prepared by light curing 3D printing.

[0045] The technical solution provided by the present disclosure has the following advantages compared with the prior art:

[0046] (1) The photosensitive resin composition provided by the present disclosure has low viscosity and fast curing speed, is suitable for light curing 3D printing technology, and has good toughness and low water absorption after curing.

[0047] (2) The denture base prepared by using the photosensitive resin composition provided by the present disclosure has low water absorption, good toughness, stable performance and strong impact resistance, and is not easy to break. DETAILED DESCRIPTION

[0048] In order to enable a clearer understanding of the above-mentioned purposes, features and advantages of the present disclosure, the solutions of the present disclosure will be further described below. It should be noted that the embodiments of the present disclosure and the features in the embodiments can be combined with each other without conflict.

[0049] Many specific details are set forth in the following description in order to provide a thorough understanding of the present disclosure. However, the present disclosure can be practiced according to other embodiments that do not require some of the specific details described below. It is understood that the present disclosure is well suited to implementing techniques described herein, but that the description is only given to a few possible embodiments.

[0050] The material information related to the following examples is shown in Table 1.

[0051] Table 1

[0052] Sample Manufacturer Model Polyurethane (Meth)acrylate 1 Sartomer CN1964 Polyurethane (Meth)acrylate 2 Dymax BR-952 Polyester Polyurethane (Meth)acrylate 1 Dymax BR-741 MD1 Polyester Polyurethane (Meth)acrylate 2 Dymax BR-742 S Hyperbranched Acrylate 1 (Functionality 6, Viscosity 1500 cps) Dymax BDT-1006 Hyperbranched Acrylate 2 Dymax BDT-1015

[0053] Example 1

[0054] The present example provides a photosensitive resin composition, the composition of which is as follows:

[0055]

[0056] In the above, the polyurethane acrylate oligomer is polyurethane (meth) acrylate 1, the monofunctional acrylate monomer is cyclohexyl acrylate, the multifunctional acrylate monomer is 1,6-hexanediol dimethacrylate, the initiator is TPO-L, the hyperbranched oligomer is hyperbranched acrylate 1, the light stabilizer is hindered amine light stabilizer HS-508 (292), and the ultraviolet light absorber is UV1990.

[0057] Example 2

[0058] The present example provides a photosensitive resin composition, the composition of which is as follows:

[0059]

[0060] In the above, the polyurethane acrylate oligomer is polyurethane (meth) acrylate 2, the monofunctional acrylate monomer is 3,3,5-trimethylcyclohexyl acrylate, the multifunctional acrylate monomer is tricyclodecane dimethanol diacrylate, the initiator is 819, the hyperbranched oligomer is hyperbranched acrylate 2, the light stabilizer is stabilizer LS-144, and the ultraviolet light absorber is UV4990.

[0061] Example 3

[0062] The present example provides a photosensitive resin composition, the composition of which is as follows:

[0063]

[0064] wherein the polyurethane acrylate oligomer is polyester polyurethane (meth) acrylate 1, the monofunctional acrylate monomer is 4-tert-butylcyclohexyl acrylate, the multifunctional acrylate monomer is dodecanediol dimethacrylate, the initiator is 2,4,6-trimethylbenzoylphenyl phosphinate ethyl ester, the hyperbranched oligomer is hyperbranched acrylate 1, the light stabilizer is Hostavin® light stabilizer 770, and the ultraviolet light absorber is UV-P.

[0065] Example 4

[0066] This example provides a photosensitive resin composition.

[0067] The difference from Example 1 is that, in this example, no hyperbranched oligomer is added.

[0068] Example 5

[0069] This example provides a photosensitive resin composition.

[0070] The difference from Example 1 is that, in this example, the multifunctional acrylate monomer used is ethoxylated bisphenol A dimethacrylate.

[0071] Comparative Example 1

[0072] This comparative example provides a photosensitive resin composition.

[0073] The difference from Example 2 is that, in this comparative example, the content of the monofunctional polyacrylate monomer is adjusted to 2 parts by weight.

[0074] Comparative Example 2

[0075] This comparative example provides a photosensitive resin composition.

[0076] The difference from Example 3 is that, in this comparative example, the content of the monofunctional polyacrylate monomer is adjusted to 30 parts by weight.

[0077] Comparative Example 3

[0078] This comparative example provides a photosensitive resin composition.

[0079] The difference from Example 2 is that, in this comparative example, the content of the multifunctional polyacrylate monomer is adjusted to 3 parts by weight.

[0080] Comparative Example 4

[0081] This comparative example provides a photosensitive resin composition.

[0082] The difference from Example 3 is that, in this comparative example, the content of the multifunctional polyacrylate monomer is adjusted to 19 parts by weight.

[0083] Application Example 1

[0084] The application example provides a denture base and a preparation method thereof.

[0085] The formula amount of each component is mixed, and the mixed resin composition is printed by using a 3D printing technology to obtain the denture base.

[0086] Performance test

[0087] The photosensitive resin composition provided by the examples and comparative examples is mixed, the viscosity of the mixture is tested, and then the water absorption, toughness and impact resistance of the cured product are tested, wherein:

[0088] (1) Viscosity: measured according to the standard “GBT2794-2013 Single Cylinder Rotational Viscosity Meter”.

[0089] (2) Water absorption: determined according to “ASTM-D570-98 Test Method for Water Absorption of Plastics”.

[0090] (3) Toughness: tested according to the elongation at break determination method in “GBT1040.1-2018 Determination Method for Tensile Properties of Plastics”.

[0091] (4) Impact resistance: tested according to “ISO180-2019 Determination Method for Notched Impact of Plastics”.

[0092] The test results are shown in Table 2:

[0093] Table 2

[0094] Sample Viscosity / cps Water Absorption / % Toughness / % Impact resistance (kJ / m 2 ) Example 1 422 1.9 5.5 2.8 Example 2 366 2.05 5.2 2.5 Example 3 905 1.82 6 2.9 Example 4 435 1.87 4.8 2.1 Example 5 472 1.95 4.6 1.9 Comparative Example 1 1280 1.85 4.1 1.7 Comparative Example 2 260 2.15 4.5 1.9 Comparative Example 3 663 2.2 5.4 1.8 Comparative Example 4 382 2.06 4.3 1.7

[0095] As can be seen from the examples and performance tests, the viscosity of the photosensitive resin composition of the present disclosure is low, the curing speed is fast, it is suitable for light curing 3D printing technology, the denture base prepared thereby is not water-absorbing, has good toughness, stable performance and strong impact resistance, and is not easy to break.

[0096] As can be seen from the comparison of Examples 1-3 and Example 4, the introduction of hyperbranched oligomers in the photosensitive resin composition can further increase the toughness of the cured product; as can be seen from the comparison of Examples 1-3 and Example 5, the use of multifunctional polyacrylate monomers without benzene rings can reduce the brittleness of the cured product and increase the toughness of the cured product. As can be seen from the comparison of Examples 1-3 and Comparative Examples 1-4, in the photosensitive resin composition provided by the present disclosure, the addition amount of each component needs to be within the range defined by the present disclosure, so that the final cured product has excellent use effect.

[0097] It should be noted that, in this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0098] The above description is merely a specific embodiment of this disclosure, enabling those skilled in the art to understand or implement it. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this disclosure. Therefore, this disclosure is not to be limited to the embodiments described herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A photosensitive resin composition, characterized by comprising: The raw materials of the photosensitive resin composition consist of the following components by weight: The hyperbranched oligomer is selected from hyperbranched acrylate BDT-1006 and / or hyperbranched acrylate BDT-1015; The polyurethane acrylate oligomer is selected from polyurethane (meth) acrylate and / or polyester polyurethane (meth) acrylate; The molecular weight of the polyurethane (meth) acrylate is 500-7000; The molecular weight of the polyester polyurethane (meth) acrylate is 2000-10000; The monofunctional acrylate monomer is selected from aliphatic monofunctional acrylate monomers containing aliphatic rings; The multifunctional acrylate monomer is selected from difunctional and / or trifunctional acrylate monomers not containing benzene rings.

2. The photosensitive resin composition according to claim 1, characterized by The monofunctional acrylate monomer is any one or a combination of at least two of isobornyl (meth) acrylate, cyclohexyl acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, and 4-tert-butylcyclohexyl acrylate.

3. The photosensitive resin composition according to claim 1, characterized by The multifunctional acrylate monomer is any one or a combination of at least two of 1,6-hexanediol di(meth) acrylate, tripropylene glycol diacrylate, diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, tripropylene glycol di(meth) acrylate, 1,12-dodecanediol dimethacrylate, and tricyclodecane dimethanol diacrylate.

4. The photosensitive resin composition according to claim 1, characterized by The initiator is selected from 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate and / or phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide.

5. The photosensitive resin composition according to claim 1, characterized by The ultraviolet light absorber is selected from ultraviolet light absorber UV-1164, ultraviolet light absorber UV-P, ultraviolet light absorber UV-1990, or ultraviolet light absorber UV-4990; And / or, the light stabilizer is selected from light stabilizer LS-144, hindered amine light stabilizer HS-508, or light stabilizer 770.

6. The photosensitive resin composition according to any one of claims 1 to 5, characterized by The viscosity of the photosensitive resin composition is 500-1200 cps.

7. Use of the photosensitive resin composition of any one of claims 1-6 in the preparation of a denture or a denture base.

8. Use according to claim 7, characterized in that, The use is in the preparation of a denture base by 3D printing.

9. A method of using the photosensitive resin composition according to any one of claims 1 to 6, characterized by, The use method comprises the following steps: mixing the formulation amount of each component, and performing photocuring.

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