Photosensitive resin composition, resin material or resin product and preparation method thereof

Abstract

The invention relates to a photosensitive resin composition, a resin material or a resin product and a preparation method thereof. The photosensitive resin composition is prepared from the following components in parts by weight: 30 to 40 parts of bifunctional aliphatic polyurethane acrylate oligomer; 60 to 70 parts of a reactive diluent; 1 to 2 parts of a photoinitiator; 1-2 parts of a defoaming agent; wherein the weight ratio of the bifunctional aliphatic polyurethane acrylate oligomer to the reactive diluent is (3: 7)-(4: 6), the reactive diluent comprises isobornyl acrylate and aliphatic monofunctional diluted acrylate, the weight ratio of the isobornyl acrylate to the aliphatic monofunctional diluted acrylate is larger than and marked as P, and P is larger than or equal to 4 / 3 and smaller than or equal to 2. The resin composition and the resin material or the resin product cured by the resin composition have excellent mechanical properties, and are suitable for the LCD technology.

Description

Technical Field

[0001] The present application relates to the technical field of photosensitive resins, and in particular to a photosensitive resin composition, a resin material or a resin product and a preparation method thereof. Background Art

[0002] 3D printing technology, also known as additive manufacturing, is mainly based on 3D digital models, and constructs objects by processing and accumulating printing materials layer by layer. Commonly used materials for 3D printing include metals, ceramics, plastics, etc.

[0003] LCD technology is a technology that uses a liquid crystal display to display the irradiation layer to cure the resin slurry. It is also a type of photocuring 3D printing technology. The principle of photocuring 3D printing technology is to use ultraviolet light to selectively cure the photosensitive resin under the control of digital signals. After curing, the resin is accumulated layer by layer until a complete 3D device is formed. Photocuring 3D printing technology has the advantages of fast speed, low energy consumption, and high precision. LCD uses the imaging principle of liquid crystal screen LCD. The computer program provides the image signal. A selective transparent area appears on the LCD screen. Ultraviolet light passes through the transparent area and irradiates the photosensitive resin in the resin tank for exposure and curing. When each layer is cured, the platform support plate lifts the cured part to allow the resin liquid to replenish and reflux. The platform drops again, and the resin is exposed and cured by ultraviolet light again. Thus, the layers are cured and raised to print exquisite three-dimensional devices.

[0004] The mechanical properties of photosensitive resins used in existing LCD technology still need to be improved. Summary of the invention

[0005] Based on this, it is necessary to provide a photosensitive resin composition, a resin material or a resin product and a preparation method thereof to improve the comprehensive mechanical properties of the resin material, especially to improve the strength of the material to be suitable for LCD technology.

[0006] In one aspect of the present application, a photosensitive resin composition is provided, comprising the following components in parts by weight:

[0007] 30 to 40 parts of difunctional aliphatic polyurethane acrylate oligomer; 60 to 70 parts of reactive diluent; 1 to 2 parts of photoinitiator; 1 to 2 parts of defoaming agent; wherein the weight ratio of the difunctional aliphatic polyurethane acrylate oligomer to the reactive diluent is 3:7 to 4:6, the reactive diluent comprises isobornyl acrylate and aliphatic monofunctional diluted acrylate, the weight ratio of isobornyl acrylate to the aliphatic monofunctional diluted acrylate is denoted as P, 4 / 3≤P≤2.

[0008] In some embodiments of the present application, the weight proportion of isobornyl acrylate is 35 to 40 parts; and / or,

[0009] The weight parts of the aliphatic monofunctional diluent acrylate are 20 parts to 30 parts.

[0010] In some embodiments of the present application, the bifunctional aliphatic polyurethane acrylate oligomer has at least one of the following characteristics (1) to (2):

[0011] (1) The weight-average molecular weight of the bifunctional aliphatic polyurethane acrylate oligomer is 20,000 to 30,000;

[0012] (2) The glass transition temperature of the bifunctional aliphatic polyurethane acrylate oligomer is 50 °C to 80 °C.

[0013] In some embodiments of the present application, the bifunctional aliphatic polyurethane acrylate oligomer is selected from Shanghai Yinchang Bifunctional YC2522.

[0014] In some embodiments of the present application, the photosensitive resin composition further includes nano-color paste. Optionally, the weight parts of the nano-color paste are 0.5 parts to 1 part.

[0015] In some embodiments of the present application, the photoinitiator is selected from one or more of benzil, benzophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone, ethyl 4-dimethylaminobenzoate, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzophenone.

[0016] In some embodiments of the present application, the defoaming agent is a UV defoaming agent. Optionally, the UV defoaming agent includes one or more of polyether defoaming agents and silicone defoaming agents.

[0017] The second aspect of the present application provides a resin material or resin product cured from the photosensitive resin composition described above.

[0018] The third aspect of the present application provides a preparation method of the resin material or resin product, which is prepared by an LCD process.

[0019] Compared with the prior art, the present application has at least the following beneficial effects:

[0020] The above photosensitive resin composition uses a bifunctional aliphatic polyurethane acrylate as an oligomer, and isobornyl acrylate and aliphatic monofunctional diluent acrylate with a ratio greater than 1:1 as active diluents, and controls the ratio of the oligomer and the active diluent in the composition to obtain a photosensitive resin composition suitable for LCD technology. The resin material prepared therefrom has high mechanical properties. Detailed Embodiments

[0021] For ease of understanding the present application, a more comprehensive description will be given below with reference to the relevant present application. Preferred embodiments of the present application are provided. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which this application belongs. The terms used in the description of this application herein are only for the purpose of describing specific embodiments and are not intended to limit this application. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0023] In this application, "first aspect", "second aspect", "third aspect", etc. are only for descriptive purposes and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features.

[0024] In this application, among the technical features described in an open-ended manner, a closed technical solution composed of the listed features is included, and an open technical solution including the listed features is also included.

[0025] In this application, "one or more" means any one, any two, or any two or more of the listed items.

[0026] In this application, regarding numerical ranges, unless otherwise specified, the above numerical ranges are considered continuous and include the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when the range refers to integers, each integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0027] Regarding the percentage content involved in this application, unless otherwise specified, for solid-liquid mixtures and solid-solid mixtures, it refers to the mass percentage, and for liquid-liquid mixtures, it refers to the volume percentage.

[0028] Regarding the percentage concentration involved in this application, unless otherwise specified, it all refers to the final concentration. The final concentration refers to the proportion of the added component in the system after adding this component.

[0029] Regarding the temperature parameters in this application, unless otherwise specified, both constant temperature treatment and treatment within a certain temperature range are allowed. The constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument.

[0030] In the present application, the method steps that do not emphasize temperature generally refer to the method steps carried out under normal temperature or room temperature conditions. In this text, normal temperature and room temperature are equivalent and interchangeable, and the specific temperature refers to 22°C to 25°C.

[0031] If there is no special instruction, all the implementation manners and optional implementation manners of the present application can be combined with each other to form a new technical solution.

[0032] If there is no special instruction, all the technical features and optional technical features of the present application can be combined with each other to form a new technical solution.

[0033] If there is no special instruction, all the steps of the present application can be carried out sequentially or randomly. For example, the method includes steps (a) and (b), which means that the method may include steps (a) and (b) carried out sequentially, or may also include steps (b) and (a) carried out sequentially. For example, it is mentioned that the method may further include step (c), which means that step (c) can be added to the method in any order. For example, the method may include steps (a), (b) and (c), or may also include steps (a), (c) and (b), or may also include steps (c), (a) and (b), etc.

[0034] If there is no special instruction, the "including" and "comprising" mentioned in the present application mean open-ended, and can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or can also mean only the components listed are included or comprised.

[0035] If there is no special instruction, in the present application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0036] In the present application, the photosensitive resin composition has the conventional meaning in the art and is a resin composition that can be cured under ultraviolet light irradiation. The resin material or resin product after curing of the photosensitive resin composition of the present application has high elasticity. Elasticity means that the photosensitive resin composition can undergo significant deformation under the action of an external force and can quickly return to a state and size close to the original state after the external force is withdrawn.

[0037] The photosensitive resin conventionally used for 3D printing mainly consists of oligomers, reactive diluents, and photoinitiators. The oligomers are the main component of the resin and determine the main properties of the cured material. The reactive diluents can adjust the viscosity and participate in the curing reaction, and also affect the properties of the cured material. The photoinitiators can absorb ultraviolet light and initiate the polymerization reaction.

[0038] Related technologies have reported soft and elastic high-performance elastomeric materials composed of polyether polyurethane acrylate oligomers, monomers, and photoinitiators, as well as methods to improve the stability and comprehensive mechanical properties of photocurable materials by doping and modifying silicon to form a network structure of silica in the resin system. The comprehensive mechanical properties of the resin materials prepared by these methods still need to be further improved.

[0039] Based on this, in the first aspect of the present application, a photosensitive resin composition is provided, which includes the following components in parts by weight:

[0040] 30 to 40 parts of difunctional aliphatic polyurethane acrylate oligomer; 60 to 70 parts of reactive diluent; 1 to 2 parts of photoinitiator; 1 to 2 parts of defoamer; wherein, the weight ratio of the difunctional aliphatic polyurethane acrylate oligomer to the reactive diluent is 4:6 to 3:7, the reactive diluent includes isobornyl acrylate and aliphatic monofunctional diluent acrylate, and the weight ratio of isobornyl acrylate to aliphatic monofunctional diluent acrylate is denoted as P, and 4 / 3 ≤ P ≤ 2.

[0041] The above photosensitive resin composition uses difunctional aliphatic polyurethane acrylate as the oligomer, and isobornyl acrylate and aliphatic monofunctional diluent acrylate with a compounding ratio greater than 1:1 as the reactive diluent, and controls the ratio of the oligomer to the reactive diluent in the composition to obtain a photosensitive resin composition suitable for LCD technology. The resin material prepared therefrom has high mechanical properties.

[0042] In some embodiments, in parts by weight, 30 to 40 parts of difunctional aliphatic polyurethane acrylate oligomer; 35 to 40 parts of isobornyl acrylate; 20 to 30 parts of aliphatic monofunctional diluent acrylate; 1 to 2 parts of photoinitiator; 1 to 2 parts of defoamer; wherein, the weight ratio of the difunctional aliphatic polyurethane acrylate oligomer to the reactive diluent is 4:6 to 3:7, and the weight ratio of isobornyl acrylate to aliphatic monofunctional diluent acrylate is greater than 1:1. When using isobornyl acrylate and aliphatic monofunctional diluent acrylate including the above parts by weight, it is beneficial for the components of the photosensitive resin composition to further play a synergistic effect and further improve the mechanical properties of the resin material.

[0043] The following details each component in the photosensitive resin composition.

[0044] Oligomer

[0045] The bifunctional aliphatic polyurethane acrylate oligomer is an acrylate oligomer containing bifunctional aliphatic polyurethane structural units, having acrylate functional groups and urethane bonds, and is obtained by the polymerization reaction of two monomers, aliphatic polyurethane and acrylate.

[0046] In some embodiments, the weight-average molecular weight of the bifunctional aliphatic polyurethane acrylate oligomer is 20,000 to 30,000, for example, but not limited to, 20,000, 21,000, 22,000, 23,000, 24,000, 25,000, 26,000, 27,000, 28,000, 29,000, 30,000, and the range between any two of the above values.

[0047] In some embodiments, the glass transition temperature of the bifunctional aliphatic polyurethane acrylate oligomer is 50°C to 80°C, for example, but not limited to, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, and the range between any two of the above values.

[0048] Examples of the bifunctional aliphatic polyurethane acrylate oligomer applicable to the present application include, but are not limited to, Shanghai Yinchang Shuangguan YC2522.

[0049] The weight parts of the bifunctional aliphatic polyurethane acrylate oligomer in the photosensitive resin composition are 30 parts to 40 parts; for example, it can be, but not limited to, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, or the range between any two of the above values.

[0050] Reactive diluent

[0051] The reactive diluent includes isobornyl acrylate and aliphatic monofunctional diluent acrylate. The weight ratio of isobornyl acrylate to aliphatic monofunctional diluent acrylate is denoted as P, and P can take 4 / 3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, and the range between any two of the above values.

[0052] Isobornyl acrylate, cas number is 5888-33-5, molecular formula is C 13 H 20 O2.

[0053] Specific examples of the aliphatic monofunctional diluent acrylate can be enumerated, but are not limited to: EBECRYL113. EBECRYL113 is a low-odor aliphatic monofunctional diluent acrylate provided by the brand supplier UCB. EBECRYL113 is the product name and model.

[0054] The weight parts of the reactive diluent in the photosensitive resin composition are from 60 parts to 70 parts; for example, it can be, but not limited to, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts or the range between any two of the above values.

[0055] In some embodiments, the weight parts of isobornyl acrylate in the photosensitive resin composition are from 35 parts to 40 parts; for example, it can be, but not limited to, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts or the range between any two of the above values.

[0056] In some embodiments, the weight parts of aliphatic monofunctional diluent acrylate in the photosensitive resin composition are from 20 parts to 30 parts; for example, it can be, but not limited to, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts or the range between any two of the above values.

[0057] In some embodiments, the weight ratio of the bifunctional aliphatic polyurethane acrylate oligomer to the reactive diluent in the photosensitive resin composition is any value between 4:6 and 3:7, such as 4:6, 7:13, 3:7.

[0058] Photoinitiator

[0059] Without limitation, the photoinitiator can be selected from one or more of benzoin, benzil, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropanone, ethyl 4-dimethylaminobenzoate, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzophenone.

[0060] The weight parts of the photoinitiator in the photosensitive resin composition are from 1 part to 2 parts; for example, it can be, but not limited to, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts or the range between any two of the above values.

[0061] Defoamer

[0062] Without limitation, the defoamer can be selected from UV defoamers, such as one or more of polyether UV defoamers and silicone UV defoamers. Specific examples can include JZ-177 of Nanjing Jiazhong Chemical Technology Co., Ltd.

[0063] The weight parts of the defoamer in the photosensitive resin composition are from 1 part to 2 parts; for example, it can be, but not limited to, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts or the range between any two of the above values.

[0064] Other additives

[0065] In some embodiments, the photosensitive resin composition of the present application may further include other additives. The additives may be additives commonly used in photosensitive resin compositions in the art, including but not limited to colorants, leveling agents, light absorbers, dispersants, antioxidants, etc. The dosages of the additives may be conventional in the art.

[0066] In some embodiments, the photosensitive resin composition of the present application further includes nano-color paste. Optionally, the weight parts of the nano-color paste are 0.5 parts to 1 part; for example, it may be, but not limited to, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 1 part, or the range between any two of the above values.

[0067] In some embodiments, the photosensitive resin composition of the present application is composed of a bifunctional aliphatic polyurethane acrylate oligomer, an active diluent, a photoinitiator, an antifoaming agent, and optionally other additives. In some embodiments, the photosensitive resin composition of the present application is composed of a bifunctional aliphatic polyurethane acrylate oligomer, an active diluent, a photoinitiator, and an antifoaming agent.

[0068] The second aspect of the present application provides a resin material or a resin product cured from the photosensitive resin composition according to any one of the embodiments of the first aspect of the present application.

[0069] The third aspect of the present application provides a method for preparing a resin material or a resin product as described in the second aspect of the present application. The resin material or the resin product is obtained by using an LCD process.

[0070] The photosensitive resin composition of the present application and the resin material or resin product cured therefrom can achieve one or more or all of the following properties:

[0071] The maximum force of the resin material measured according to ASTM D638-14 ≥ 90 N;

[0072] The breaking force of the resin material measured according to ASTM D638-14 ≥ 85 N;

[0073] The tensile strength of the resin material measured according to ASTM D638-14 ≥ 3 MPa;

[0074] The tensile elastic modulus of the resin material measured according to ASTM D638-14 ≥ 20 MPa;

[0075] The elongation at break of the resin material measured according to ASTM D638-14 ≥ 180%.

[0076] The following are specific embodiments. The purpose is to further explain the present application in detail to help the technical personnel and researchers in the field to further understand the present application. The relevant technical conditions do not constitute any limitation to the present application. Any form of modification made within the scope of the claims of the present application is within the scope of protection of the claims of the present application.

[0077] Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods. Experimental methods without specific conditions specified in the examples are carried out according to conventional conditions, such as those described in literature or books or methods recommended by manufacturers.

[0078] The reagents involved are as follows:

[0079] The bifunctional aliphatic polyurethane acrylate oligomer was Shanghai Yinchang Bifunctional YC2522;

[0080] Isobornyl acrylate was from Shanghai Yinchang IBOA;

[0081] The aliphatic monofunctional diluted acrylate is allnex EBECRYL113;

[0082] The UV defoamer is JZ-177 from Nanjing Jiazhong Chemical Technology Co., Ltd.

[0083] Example 1

[0084] (a) 40 parts by weight of a difunctional aliphatic polyurethane acrylate oligomer, 40 parts by weight of isobornyl acrylate and 20 parts by weight of EBECRYL 113 were mixed and stirred uniformly.

[0085] (b) Add 2 parts by weight of a photoinitiator, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, and 1 part by weight of a nano-color paste, stir evenly in a 60° C. water bath, add 2 parts by weight of a UV defoamer, place in an ultrasonic cleaner for defoaming treatment for 1 hour, and obtain a photosensitive resin composition.

[0086] (c) Using an LCD 3D printer, the photosensitive resin composition obtained in step (b) was 3D printed at a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, a bottom layer number of 3, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s to obtain a resin product.

[0087] Example 2

[0088] (a) 30 parts by weight of bifunctional aliphatic polyurethane acrylate oligomer, 40 parts by weight of isobornyl acrylate and 30 parts by weight of EBECRYL 113 were mixed and stirred uniformly.

[0089] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of the UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain the photosensitive resin composition.

[0090] (c) Using an LCD 3D printer, perform 3D printing with the photosensitive resin composition obtained in step (b) under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s to obtain a resin product.

[0091] Comparative Example 1

[0092] (a) Mix 33.3 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 33.3 parts by weight of isobornyl acrylate, and 33.3 parts by weight of EBECRYL 113, and stir evenly.

[0093] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of the UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain the photosensitive resin composition.

[0094] (c) Using an LCD 3D printer, perform 3D printing with the photosensitive resin composition obtained in step (b) under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s to obtain a resin product.

[0095] Comparative Example 2

[0096] (a) Mix 20 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 30 parts by weight of isobornyl acrylate, and 50 parts by weight of EBECRYL 113, and stir evenly.

[0097] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of the UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain the photosensitive resin composition.

[0098] (c) Using an LCD 3D printer, under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s, perform 3D printing using the photosensitive resin composition obtained in step (b) to obtain a resin product.

[0099] Comparative Example 3

[0100] (a) Mix 20 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 40 parts by weight of isobornyl acrylate, and 40 parts by weight of EBECRYL 113, and stir evenly.

[0101] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of a UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain a photosensitive resin composition.

[0102] (c) Using an LCD 3D printer, under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s, perform 3D printing using the photosensitive resin composition obtained in step (b) to obtain a resin product.

[0103] Comparative Example 4

[0104] (a) Mix 20 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 50 parts by weight of isobornyl acrylate, and 30 parts by weight of EBECRYL 113, and stir evenly.

[0105] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of a UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain a photosensitive resin composition.

[0106] (c) Using an LCD 3D printer, under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s, perform 3D printing using the photosensitive resin composition obtained in step (b) to obtain a resin product.

[0107] Comparative Example 5

[0108] (a) Mix 40 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 20 parts by weight of isobornyl acrylate, and 40 parts by weight of EBECRYL 113, and stir evenly.

[0109] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of a UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain a photosensitive resin composition.

[0110] (c) Use an LCD 3D printer to perform 3D printing with the photosensitive resin composition obtained in step (b) under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s to obtain a resin product.

[0111] Comparative Example 6

[0112] (a) Mix 40 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 30 parts by weight of isobornyl acrylate, and 30 parts by weight of EBECRYL 113, and stir evenly.

[0113] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of a UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain a photosensitive resin composition.

[0114] (c) Use an LCD 3D printer to perform 3D printing with the photosensitive resin composition obtained in step (b) under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s to obtain a resin product.

[0115] Comparative Example 7

[0116] (a) Mix 35 parts by weight of a bifunctional aliphatic polyurethane acrylate oligomer, 35 parts by weight of isobornyl acrylate, and 30 parts by weight of EBECRYL 113, and stir evenly.

[0117] (b) Add 2 parts by weight of the photoinitiator diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide and 1 part by weight of the nano-color paste, stir evenly in a water bath at 50 - 60 °C, add 2 parts by weight of the UV defoamer, and place it in an ultrasonic cleaner for defoaming treatment for 1 h to obtain the photosensitive resin composition.

[0118] (c) Use an LCD 3D printer to perform 3D printing with the photosensitive resin composition obtained in step (b) under the conditions of a wavelength of 405 nm, an LED power of 75%, a layer thickness of 0.050 mm, an exposure time of 6.500 s, a cooling time of 5.000 s, 3 bottom layers, a bottom exposure time of 15.000 s, and a bottom cooling time of 10.000 s to obtain a resin product.

[0119] The weight parts of the raw material oligomers, active diluents, photoinitiators, and defoamers in the preparation methods of Examples 1 - 2 and Comparative Examples 1 - 7 are listed in Table 1 below:

[0120] Table 1

[0121]

[0122] The resin products prepared in Examples 1 - 2 and Comparative Examples 1 - 7 were subjected to mechanical property tests, and the test results are shown in Table 2 below.

[0123] Among them, the test conditions or test standards for each performance test item refer to ASTM D638 - 14.

[0124] Table 2

[0125]

[0126] As can be seen from Table 2 above, the photosensitive resin composition provided by this application and the resin material or resin product cured therefrom have excellent comprehensive mechanical properties, especially excellent maximum force performance.

[0127] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered to be within the scope described in this specification.

[0128] The above-described embodiments merely represent several implementation manners of the present application, facilitating the specific and detailed understanding of the technical solution of the present application, but should not be construed as a limitation on the protection scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can be made, and these all fall within the protection scope of the present application. It should be understood that the technical solutions obtained by those skilled in the art through logical analysis, reasoning or limited experiments based on the technical solutions provided by the present application are all within the protection scope of the appended claims of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A photosensitive resin composition, characterized in that, Comprising the following components by weight parts: 30 to 40 parts of bifunctional aliphatic polyurethane acrylate oligomer; 60 to 70 parts of reactive diluent; 1 to 2 parts of photoinitiator; 1 to 2 parts of defoamer; Wherein, the weight ratio of the bifunctional aliphatic polyurethane acrylate oligomer to the reactive diluent is 3:7 to 4:6, the reactive diluent includes isobornyl acrylate and aliphatic monofunctional diluent acrylate, and the weight ratio of the isobornyl acrylate to the aliphatic monofunctional diluent acrylate is denoted as P, and 4 / 3 ≤ P ≤ 2.

2. The photosensitive resin composition according to claim 1, wherein The weight parts of the isobornyl acrylate are 35 to 40 parts; and / or, The weight parts of the aliphatic monofunctional diluent acrylate are 20 to 30 parts.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that, The weight average molecular weight of the bifunctional aliphatic polyurethane acrylate oligomer is 20,000 to 30,000.

4. The photosensitive resin composition according to claim 1 or 2, characterized in that, The glass transition temperature of the bifunctional aliphatic polyurethane acrylate oligomer is 50°C to 80°C.

5. The photosensitive resin composition according to claim 1, characterized in that, The bifunctional aliphatic polyurethane acrylate oligomer is selected from Shanghai Yinchang Shuangguan YC2522.

6. The photosensitive resin composition according to claim 1, wherein Also includes nano-color paste. Optionally, the weight parts of the nano-color paste are 0.5 to 1 part.

7. The photosensitive resin composition according to claim 1, wherein The photoinitiator is selected from one or more of benzil, benzophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholin-1-propanone, ethyl 4-dimethylaminobenzoate, 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and benzophenone.

8. The photosensitive resin composition according to claim 1, characterized in that, The defoamer is a UV defoamer. Optionally, the UV defoamer includes one or more of polyether defoamers and silicone defoamers.

9. A resin material or resin product cured from the photosensitive resin composition according to any one of claims 1 to 8.

10. A method for preparing the resin material or resin product as described in claim 9, characterized in that, Prepared by the LCD process.

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