Photocurable resin composition, method for preparing the same, and use thereof, photocurable resin material and use thereof

Abstract

The present application relates to the technical field of organic photocuring, and discloses a photocuring resin composition, a preparation method thereof, and a photocuring resin material prepared from the photocuring resin composition. The composition comprises, in parts by weight, 20-40 parts of modified epoxy acrylate, 15-35 parts of aliphatic polyurethane acrylate, 25-40 parts of active diluent, 3-5 parts of photoinitiator, and 4-10 parts of toughening agent, wherein the toughening agent is selected from hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber. The photocuring resin composition uses hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber as the toughening agent, which can significantly reduce the volume shrinkage of the photocuring resin composition during curing, and ensure the dimensional stability of the prepared photocuring resin material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic photocuring, in particular, to a photocuring resin composition and a preparation method thereof, a photocuring resin material prepared from the photocuring resin composition and an application of the photocuring resin material. BACKGROUND

[0002] Photocuring refers to a process in which a liquid chemical formula (such as a coating, ink or adhesive) is rapidly converted into a solid state under the action of high-intensity light energy. This industry has been rapidly developing in recent years due to its advantages of being fast and efficient, protecting the environment and saving energy. At present, photocuring has become a link in the world's industrial chain. However, the polymer crosslinking density of the liquid photocuring resin material is high, the molded parts are brittle and have poor toughness, and the cured product will crack due to deformation and stress concentration when the temperature changes sharply, thus it is difficult to meet the ideal industrial requirements, so it is crucial to improve the toughness and strength of the photocured photocuring resin material.

[0003] Liquid rubber, especially end-functional liquid rubber, has been successfully used as a toughening modifier for epoxy resin, phenolic resin and unsaturated polyester resin. The combination of liquid rubber and photocuring resin material expands its application space.

[0004] CN101200527A discloses a preparation method of liquid rubber modified epoxy acrylate prepolymer. The end-hydroxyl polybutadiene liquid rubber is reacted with maleic anhydride to obtain an end-carboxyl liquid rubber prepolymer, and then the end-carboxyl liquid rubber prepolymer is reacted with an epoxy acrylate resin to obtain a liquid rubber modified epoxy acrylate prepolymer. The photocuring coating prepared from the prepolymer has good hand feeling and elastic properties.

[0005] CN105482059A relates to a preparation method of an end-hydroxyl polybutadiene modified ultraviolet photocuring waterborne polyurethane. Under the action of a catalyst and heating and stirring at 45℃, an aliphatic diisocyanate is reacted with a polyester polyol and an end-hydroxyl polybutadiene for 2.5h to obtain product (A). The temperature is raised to 70℃, a monomer containing both -OH and -COOH groups is added to the reaction system, and the product (A) is reacted for 3h to obtain product (B). The temperature is maintained at 70℃, and a monomer containing both -OH and -C=C groups is continuously added to the reaction system, and the product (B) is reacted for 3.5h to obtain product (C), i.e. an end-hydroxyl polybutadiene modified ultraviolet photocuring waterborne polyurethane. The prepared resin has excellent heat resistance, weather resistance and mechanical properties.

[0006] In the above-mentioned patents, the liquid rubber is usually used as a modifier for modifying the epoxy acrylate or polyurethane prepolymer that can participate in photocuring reaction, so as to improve the mechanical properties of the photocuring material.

[0007] In the current related reports, there is a method of using liquid rubber to toughen the photocuring material. That is, the epoxidized hydroxyl-terminated polybutadiene liquid rubber is directly added to the free radical-cationic hybrid photocuring reaction system as a toughening agent, mixed uniformly and cured, and the toughening of the cured material is realized.

[0008] CN105399905A discloses a photocuring three-dimensional printing material with good toughness and high impact strength and a preparation method thereof. The photocuring three-dimensional printing material uses epoxidized hydroxyl-terminated polybutadiene liquid rubber with a molecular weight of 3000-3600 as a toughening agent. The toughening agent introduces epoxy groups on the flexible hydroxyl-terminated polybutadiene segment and participates in the photocuring reaction by cationic initiation and free radical initiation simultaneous polymerization, and forms an interpenetrating network structure with the resin, thereby improving the toughness of the resin matrix. Currently, there is no report on the direct use of hydroxyl-terminated or hydroxyl-terminated epoxidized polyolefin liquid rubber in a free radical photocuring reaction system. SUMMARY

[0009] The purpose of the present application is to overcome the shortcomings of the prior art, provide a photocuring resin composition, a preparation method thereof and a photocuring resin material prepared from the photocuring resin composition. The photocuring resin composition uses hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber as a toughening agent, which can significantly reduce the volume shrinkage of the photocuring resin composition during curing and ensure that the prepared photocuring resin material has excellent dimensional stability.

[0010] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a photocuring resin composition, characterized in that, in terms of weight parts, the composition comprises:

[0011] polyester-modified epoxy acrylate 20-40 parts; aliphatic polyurethane acrylate 15-35 parts; active diluent 25-40 parts; photoinitiator 3-5 parts; toughening agent 4-10 parts;

[0012] The toughening agent is selected from hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber.

[0013] The second aspect of the present application provides a preparation method of the above-mentioned photocuring resin composition, characterized in that the method comprises the following steps:

[0014] (1) mixing the active diluent, the photoinitiator and the optional co-initiator under light shielding conditions until the initiator is completely dissolved to obtain a mixed solution;

[0015] (2) adding the modified epoxy acrylate, the polyurethane acrylate prepolymer and the toughening agent to the mixed solution under light shielding conditions, and stirring to obtain a photocuring resin composition.

[0016] A third aspect of the present invention provides a photocurable resin material, characterized in that the photocurable resin material is prepared from the above-mentioned photocurable resin composition.

[0017] The fourth aspect of the present invention provides the application of the above-described photocurable resin composition or the above-described photocurable resin material in the field of photocurable rapid prototyping.

[0018] Through the above technical solutions, the photocurable resin composition, its preparation method and application, and the photocurable resin material prepared from the photocurable resin composition provided by the present invention achieve the following beneficial effects:

[0019] In the photocurable resin composition provided by the present invention, hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber are used as toughening agents, thereby significantly reducing the volume shrinkage of the photocurable resin composition during curing and ensuring that the obtained photocurable resin material has excellent dimensional stability.

[0020] Furthermore, the preparation process of the photocurable resin composition provided by the present invention is simple, solvent-free, and easy to adjust the viscosity, thereby improving the performance of the photocurable resin composition and further expanding its application fields. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] The first aspect of the present invention provides a photocurable resin composition, characterized in that, by weight, the composition comprises: 20-40 parts of polyester-modified epoxy acrylate; 15-35 parts of aliphatic polyurethane acrylate; 25-40 parts of reactive diluent; 3-5 parts of photoinitiator; and 4-10 parts of toughening agent.

[0023] The toughening agent is selected from hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber.

[0024] In this invention, using hydroxyl-terminated polyolefin liquid rubber and / or hydroxyl-terminated epoxidized polyolefin liquid rubber as toughening agents can significantly reduce the volume shrinkage of the photocurable resin composition during curing, ensuring that the obtained photocurable resin material has excellent dimensional stability, and increasing the flexibility, impact strength, and tensile strength of the obtained photocurable resin material while reducing the pencil hardness.

[0025] In particular, in the present application, the active diluent is contained in the composition in a specific amount, which can make the composition have a suitable viscosity, thereby improving the processability of the composition and making the photocured resin material prepared from the composition have excellent mechanical properties. Specifically, when the amount of the active diluent is small, the viscosity of the system is large, which is not conducive to rapid prototyping; when the amount of the active diluent is too large, the curing reaction speed is slow, and the mechanical properties of the molded product are poor.

[0026] According to the present application, the composition comprises, in parts by weight: 20-35 parts of polyester-modified epoxy acrylate; 30-35 parts of aliphatic polyurethane acrylate; 25-35 parts of active diluent; 3-5 parts of photoinitiator; and 5-8 parts of toughening agent.

[0027] According to the present application, the number average molecular weight of the toughening agent is 1000-30,000.

[0028] In the present application, the hydroxyl-terminated polyolefin liquid rubber and / or the hydroxyl-terminated epoxidized polyolefin liquid rubber having a number average molecular weight within the above range are used as the toughening agent for the photocured resin composition, which can make the liquid rubber disperse well in the resin and have a good interpenetrating network with the resin matrix, thereby greatly improving the toughness and other mechanical properties of the photocured resin composition.

[0029] Further, the number average molecular weight of the toughening agent is 2,000-10,000.

[0030] According to the present application, the toughening agent is at least one selected from the group consisting of hydroxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated epoxidized polybutadiene liquid rubber, hydroxyl-terminated polyisoprene liquid rubber, hydroxyl-terminated epoxidized polyisoprene liquid rubber, hydroxyl-terminated polybutene liquid rubber, and hydroxyl-terminated epoxidized polybutene liquid rubber.

[0031] In the present application, the content of the epoxy group in the hydroxyl-terminated epoxidized polyolefin liquid rubber is 5-15 wt% based on the total mass of the hydroxyl-terminated epoxidized polyolefin liquid rubber.

[0032] According to the present application, the functionality of the polyester-modified epoxy acrylate is 2-4, and the viscosity of the polyester-modified epoxy acrylate is 3000-6500 cps under the conditions of a solid content of 100 wt% and a temperature of 60℃.

[0033] According to the present application, the functionality of the aliphatic polyurethane acrylate is 2-3, and the viscosity of the aliphatic polyurethane acrylate is 10000-20000 cps under the conditions of a solid content of 100 wt% and a temperature of 25℃.

[0034] According to the present application, the reactive diluent is at least one selected from the group consisting of tripropyleneglycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane trimethacrylate (TMPTMA), ethoxylated trimethylolpropane triacrylate (EOTMPTA), isooctyl acrylate and pentaerythritol triacrylate (PETA).

[0035] In the present application, the use of the above-mentioned specific type of reactive diluent in the photocuring resin composition can achieve control of the viscosity of the composition, and further improve the comprehensive performance of the photocuring resin material prepared from the composition.

[0036] According to the present application, the reactive diluent is at least one selected from the group consisting of tripropyleneglycol diacrylate (TPGDA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane trimethacrylate (TMPTMA), ethoxylated trimethylolpropane triacrylate (EOTMPTA), isooctyl acrylate and pentaerythritol triacrylate (PETA).

[0037] According to the present application, the photoinitiator is at least one selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenylpropanone (1173), (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (TPO), a mixture of 2-isopropylthioxanthone (ITX) and ethyl 4-dimethoxybenzoate (EDAB), and a mixture of benzophenone (BP) and ethyl 4-dimethoxybenzoate (EDAB).

[0038] In the present application, when the photoinitiator is a mixture of 2-isopropylthioxanthone and ethyl 4-dimethoxybenzoate, the mass ratio of 2-isopropylthioxanthone to ethyl 4-dimethoxybenzoate is not particularly limited, and the conventional amount in the art can be used. Specifically, the mass ratio of 2-isopropylthioxanthone to ethyl 4-dimethoxybenzoate is 2:1.

[0039] In the present application, when the photoinitiator is a mixture of benzophenone and ethyl 4-dimethoxybenzoate, the mass ratio of benzophenone to ethyl 4-dimethoxybenzoate is not particularly limited, and the conventional amount in the art can be used. Specifically, the mass ratio of 2-isopropylthioxanthone to ethyl 4-dimethoxybenzoate is 2:1.

[0040] The second aspect of the present application provides a preparation method of the above-mentioned photocuring resin composition, characterized in that the method comprises the following steps:

[0041] (1) mixing the active diluent, the photoinitiator and the optional co-initiator under light-proof condition until the initiator is completely dissolved to obtain a mixed solution;

[0042] (2) adding the polyester-modified epoxy acrylate, the aliphatic polyurethane acrylate prepolymer and the toughening agent into the mixed solution under light-proof condition, and stirring to obtain the photocuring resin composition.

[0043] In the present application, the preparation method of the photocuring resin composition has the advantages of simple process and no need of solventization, so that the viscosity of the composition is easy to adjust, and the photocuring resin composition obtained by the method and the photocuring resin material prepared from the photocuring resin composition have improved performance and can meet the needs of different fields.

[0044] In the present application, the preparation method further comprises weighing the raw materials according to the weight ratio at room temperature.

[0045] According to the present application, in step (2), the stirring conditions include a stirring temperature of 40-60°C and a stirring time of 1-2h.

[0046] In the present application, in order to avoid the adverse effects of light in the environment on the performance of the photocuring resin composition, preferably, the preparation method further comprises placing the photocuring resin composition in a dark environment for standing and defoaming.

[0047] The third aspect of the present application provides a photocuring resin material, characterized in that the photocuring resin material is prepared from the photocuring resin composition.

[0048] In the present application, the photocuring resin composition can be cured by using conventional methods in the art to prepare the photocuring resin material.

[0049] In one specific embodiment of the present application, the photocuring resin material is prepared by the following steps: dropping the photocuring resin composition onto a glass sheet, controlling the thickness of the cured layer to be 0.2-0.5mm, placing it in a UV curing machine for photocuring to obtain the photocuring resin material.

[0050] In the present application, the photocuring conditions include a power of the UV curing machine of 1000-1500W, a main emission wavelength of 365nm and 385nm, an irradiation distance of 20-25cm, and a temperature of 20-30°C.

[0051] The fourth aspect of the present application provides the use of the photocuring resin material in the field of photocuring rapid prototyping.

[0052] The present application will be described in detail by the following examples. In the following examples,

[0053] Curing time: The liquid resin was coated on a glass sheet with a wire bar applicator to a wet film thickness of 0.5 mm, and cured in a UV curing machine. The curing time was measured by the touch dry method.

[0054] Flexibility: A QTX type paint film elasticity tester was used, which was composed of 6 steel rods with different diameters. Each rod was 35 mm long, and the curvature radiuses were 0.5 mm, 1 mm, 1.5 mm, 2 mm, 2.5 mm, 5 mm, and 7.5 mm, respectively. A tinplate with a size of 120 mm x 25 mm x 0.2 mm was selected. The photocured film was placed with the film surface facing upwards, and the sample plate was tightly pressed on the rod with the diameter used. The sample plate was bent around the rod within 2-3 s, and the two thumbs should be symmetric to the center line of the rod after bending. Then, the damage phenomena of the paint film, such as mottling, cracking, and peeling, were observed. The minimum diameter of the rod on which the sample plate was bent without causing damage to the paint film represented the flexibility of the paint film.

[0055] Impact strength: The test was performed according to the standard GB / T1043.1-2008.

[0056] Elongation at break: Five samples with a size of 60 x 10 x 4 mm were prepared according to the type I sample in GB / T1042-92. 3 The dumbbell-shaped sample was tested for the elongation at break of the cured material using a universal mechanical tester at a loading speed of 5 mm / min.

[0057] Pencil hardness: The test was performed according to the standard [GB6739-1996] pencil method for measuring the hardness of a paint film.

[0058] Volume shrinkage: The density of the resin system before curing ρ1 and the density after complete curing ρ2 were measured at room temperature using a specific gravity bottle method. Then, the volume shrinkage % = (ρ2-ρ1) / ρ2 x 100%.

[0059] Polyester-modified epoxy acrylate, solid content 100 wt%, functionality 2, viscosity 5500 cps at 60°C, Guangzhou Chenglan Material Technology Co., Ltd.;

[0060] Aliphatic polyurethane acrylate, functionality 3, solid content 100 wt%, viscosity 12000 cps at 25°C, Guangzhou Chenglan Material Technology Co., Ltd.;

[0061] Toughening agent I, hydroxyl-terminated polybutadiene liquid rubber, number average molecular weight 2000, self-made;

[0062] Toughening agent II, hydroxyl-terminated epoxidized polybutadiene liquid rubber, number average molecular weight 7200, epoxy group content 12 wt%, self-made;

[0063] Toughening agent III, hydroxyl-terminated epoxidized polyisoprene liquid rubber, number average molecular weight of 5000, content of epoxy groups of 15 wt%, self-made;

[0064] Toughening agent IV, hydroxyl-terminated epoxidized polybutadiene liquid rubber, number average molecular weight of 10000, content of epoxy groups of 5 wt%, self-made;

[0065] Toughening agent V, hydroxyl-terminated polyisoprene liquid rubber, number average molecular weight of 2400, self-made;

[0066] Toughening agent VI, hydroxyl-terminated polybutadiene liquid rubber, number average molecular weight of 5600, self-made;

[0067] The other raw materials used in the examples and comparative examples are commercially available.

[0068] Example 1

[0069] In parts by mass, 25 parts of reactive diluents, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts, were added into a container, and magnetically stirred under light-avoiding condition until the photoinitiators were completely dissolved; then 35 parts of polyester-modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate, and 5 parts of toughening agent I were added into the mixed solution prepared in the above step, and stirred at 50°C under light-avoiding condition for 2h; after the components were mixed uniformly, a photocuring resin composition A1 was obtained, which was placed in a dark environment for standing and defoaming for use.

[0070] Example 2

[0071] In parts by mass, 25 parts of reactive diluents, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts, were added into a container, and magnetically stirred under light-avoiding condition until the photoinitiators were completely dissolved; then 35 parts of polyester-modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate, and 5 parts of toughening agent II were added into the mixed solution prepared in the above step, and stirred at 50°C under light-avoiding condition for 2h; after the components were mixed uniformly, a photocuring resin composition A2 was obtained, which was placed in a dark environment for standing and defoaming for use.

[0072] Example 3

[0073] In parts by mass, 25 parts of reactive diluents, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiators were completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate and 8 parts of toughening agent II were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h, and after the components were uniformly mixed, a photocuring resin composition A3 was obtained, which was placed in a dark environment for standing and defoaming for standby use.

[0074] Example 4

[0075] In parts by mass, 25 parts of reactive diluents, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiators were completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate and 8 parts of toughening agent II were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h, and after the components were uniformly mixed, a photocuring resin composition A3 was obtained, which was placed in a dark environment for standing and defoaming for standby use.

[0076] Example 5

[0077] In parts by mass, 25 parts of reactive diluents, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiators were completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate and 8 parts of toughening agent II were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h, and after the components were uniformly mixed, a photocuring resin composition A3 was obtained, which was placed in a dark environment for standing and defoaming for standby use.

[0078] Example 6

[0079] In parts by mass, 25 parts of reactive diluents, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiators were completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate and 8 parts of toughening agent II were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h, and after the components were uniformly mixed, a photocuring resin composition A3 was obtained, which was placed in a dark environment for standing and defoaming for standby use.

[0080] Example 7

[0081] In mass parts, 35 parts of reactive diluents, including TPGDA 15 parts, HDDA 10 parts, PETA 10 parts, 1173 photoinitiator 5 parts were added into the container respectively, and stirred magnetically under light-proof condition until the photoinitiator was completely dissolved; then modified epoxy acrylate 20 parts and polyurethane acrylate prepolymer 35 parts and toughening agent IV 5 parts (number average molecular weight 10000 g / mol, epoxidation rate 5%) were added into the mixed solution prepared in the above step respectively, and stirred magnetically under light-proof condition at 50°C for 2h, after the components were mixed uniformly, the photocuring resin composition A7 was obtained, and placed in a dark environment for standing and defoaming before use.

[0082] Example 8

[0083] In mass parts, 25 parts of reactive diluents, including TPGDA 10 parts, HDDA 10 parts, TMPTMA 5 parts, photoinitiator 2-isopropylthioxanthone (ITX) 4 parts, 4-dimethylamino ethyl benzoate (EDAB) 2 parts were added into the container respectively, and stirred magnetically under light-proof condition until the photoinitiator was completely dissolved; then modified epoxy acrylate 40 parts and polyurethane acrylate prepolymer 20 parts and toughening agent V 9 parts were added into the mixed solution prepared in the above step respectively, and stirred magnetically under light-proof condition at 50°C for 2h, after the components were mixed uniformly, the photocuring resin composition A8 was obtained, and placed in a dark environment for standing and defoaming before use.

[0084] Example 9

[0085] In mass parts, 40 parts of reactive diluents, including TPGDA 15 parts, HDDA 15 parts, TMPTMA 10 parts, photoinitiator ITX 4 parts, EDAB 2 parts were added into the container respectively, and stirred magnetically under light-proof condition until the photoinitiator was completely dissolved; then modified epoxy acrylate 35 parts and polyurethane acrylate 15 parts and toughening agent VI 4 parts were added into the mixed solution prepared in the above step respectively, and stirred magnetically under light-proof condition at 50°C for 2h, after the components were mixed uniformly, the photocuring resin composition A9 was obtained, and placed in a dark environment for standing and defoaming before use.

[0086] Example 10

[0087] In mass parts, 40 parts of reactive diluents, including TPGDA 15 parts, HDDA 15 parts, EOTMPTA 10 parts, photoinitiator BP 4 parts, EDAB 2 parts were added into the container respectively, and stirred magnetically under light-proof condition until the photoinitiator was completely dissolved; then modified epoxy acrylate 35 parts and polyurethane acrylate 15 parts and toughening agent IV 4 parts were added into the mixed solution prepared in the above step respectively, and stirred magnetically under light-proof condition at 50°C for 2h, after the components were mixed uniformly, the photocuring resin composition A10 was obtained, and placed in a dark environment for standing and defoaming before use.

[0088] Comparative Example 1

[0089] In mass parts, 25 parts of active diluent, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiator was completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h; after the components were uniformly mixed, a photocuring resin composition D1 was obtained, which was placed in a dark environment for standing and defoaming.

[0090] Comparative Example 2

[0091] In mass parts, 25 parts of active diluent, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiator was completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h; after the components were uniformly mixed, a photocuring resin composition D1 was obtained, which was placed in a dark environment for standing and defoaming.

[0092] Comparative Example 3

[0093] In mass parts, 25 parts of active diluent, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiator was completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h; after the components were uniformly mixed, a photocuring resin composition D1 was obtained, which was placed in a dark environment for standing and defoaming.

[0094] Comparative Example 4

[0095] In mass parts, 25 parts of active diluent, including TPGDA 16 parts, HDDA 6 parts, TMPTMA 3 parts, photoinitiator 184 and TPO each 2.5 parts were added into a container, and magnetic stirring was carried out under light-proof condition until the photoinitiator was completely dissolved; then 35 parts of polyester modified epoxy acrylate and 30 parts of aliphatic polyurethane acrylate were added into the mixed solution prepared in the above step, and stirring was carried out under light-proof condition at 50°C for 2h; after the components were uniformly mixed, a photocuring resin composition D1 was obtained, which was placed in a dark environment for standing and defoaming.

[0096] Comparative Example 5

[0097] Into a container, 16 parts of reactive diluents, including TPGDA 9 parts, HDDA 5 parts, EOTMPTA 2 parts, photoinitiator BP 4 parts, reactive amine co-initiator EDAB 2 parts were added respectively, and magnetically stirred under light-proof condition until the photoinitiator was completely dissolved; then the modified epoxy acrylate 35 parts and polyurethane acrylate 15 parts and 4 parts of toughening agent IV were added into the mixed solution prepared in the above step, and stirred at 50°C under light-proof condition for 2h. After the components were mixed uniformly, the photocuring resin composition D5 was obtained, and placed in a dark environment for standing and defoaming for use.

[0098] Test Example

[0099] An appropriate amount of photocuring resin compositions A1-A10 and D1-D5 were added dropwise onto a glass sheet, and a cured layer with a thickness of 0.5mm was obtained. Then, the glass sheet was placed in a 1000W ultraviolet light curing machine (main emission wavelength of 365nm and 385nm, irradiation distance of 20cm), and cured at room temperature to obtain a photocuring resin material. The properties of the photocuring resin were tested, and the results are shown in Table 1.

[0100] Table 1

[0101] Curing time / s Flexibility / mm Impact strength / KJ m 2 ]] Elongation at break / % Pencil hardness Volume shrinkage / % A1 22 1.5 30.1 38.0 4H 3.2 A2 24 1.5 38.5 43.6 4H 3.8 A3 20 1.0 43.1 48.2 3H 3.1 A4 20 1.5 40.3 44.8 4H 3.1 A5 20 1.5 30.6 37.9 4H 3.9 A6 20 1.0 33.2 38.8 3H 4.1 A7 22 1.0 35.1 40.0 2H 4.5 A8 18 1.5 32.1 38.6 4H 4.0 A9 15 1.5 29.8 37.5 4H 4.6 A10 25 1.5 23.5 37.1 4H 5.4 D1 30 2.5 14.7 13.5 6H 5.5 D2 28 2.5 16.9 16.4 5H 4.9 D3 35 2.0 22.9 24.3 5H 4.3 D4 38 1.5 17.1 21.4 4H 5.1 D5 10 2.0 8.5 10.6 5H 5.6

[0102] As can be seen from Table 1, the photocuring resin material prepared from the photocuring resin composition provided by the present application has a proper curing time, low flexibility, high impact strength, high elongation at break, low pencil hardness and low volume shrinkage, thus indicating that the photocuring material prepared from the photocuring resin composition provided by the present application has excellent mechanical properties, flexibility, hardness and dimensional stability.

[0103] As can be seen from Example 2, Example 5 and Comparative Example 3, the influence of the comprehensive performance of the photocuring resin material containing the terminal hydroxyl group and / or terminal hydroxyl epoxy polyolefin liquid rubber is better than that of the same amount of silane modified SiO2 nanoparticles.

[0104] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application, and fall within the protection scope of the present application.

Claims

1. A photocurable resin composition, characterized by, The composition comprises, by weight: 20-35 parts of polyester modified epoxy acrylate; 30-35 parts of aliphatic polyurethane acrylate; 25-35 parts of reactive diluent; 3-5 parts of photoinitiator; 5-10 parts of toughening agent; The toughening agent is selected from at least one of hydroxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated epoxidized polybutadiene liquid rubber, hydroxyl-terminated polyisoprene liquid rubber, hydroxyl-terminated epoxidized polyisoprene liquid rubber, hydroxyl-terminated polybutadiene liquid rubber, and hydroxyl-terminated epoxidized polybutadiene liquid rubber. The polyester modified epoxy acrylate has a functionality of 2-4 and a viscosity of 3000-6500 cps at a solid content of 100 wt% and 60℃. The aliphatic polyurethane acrylate has a functionality of 2-3 and a viscosity of 10000-20000 cps at a solid content of 100 wt% and 25℃. The content of epoxy groups in the hydroxyl-terminated epoxidized polybutadiene liquid rubber is 5-15 wt% based on the total mass of the hydroxyl-terminated epoxidized polybutadiene liquid rubber.

2. The photocurable resin composition according to claim 1, wherein, The number average molecular weight of the toughening agent is 5,000-10,000.

3. The photocurable resin composition according to claim 1 or 2, wherein, The toughening agent is selected from at least one of hydroxyl-terminated polybutadiene liquid rubber, hydroxyl-terminated epoxidized polybutadiene liquid rubber, hydroxyl-terminated polyisoprene liquid rubber, hydroxyl-terminated epoxidized polyisoprene liquid rubber, hydroxyl-terminated polybutadiene liquid rubber, and hydroxyl-terminated epoxidized polybutadiene liquid rubber.

4. The photocurable resin composition according to claim 1 or 2, wherein, The reactive diluent is selected from at least one of tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, isooctyl acrylate, and pentaerythritol triacrylate.

5. The photocurable resin composition according to claim 4, wherein, The reactive diluent is tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane trimethacrylate, and the amount ratio of the tripropyleneglycol diacrylate, 1,6-hexanediol diacrylate, and trimethylolpropane trimethacrylate is 10-16:6-15:3-10.

6. The photocurable resin composition according to claim 1 or 2, wherein, The photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide, a mixture of 2-isopropylthioxanthone and ethyl 4-dimethoxybenzoate, and a mixture of benzophenone and ethyl 4-dimethoxybenzoate.

7. A method for producing the photocurable resin composition according to any one of claims 1 to 6, characterized by, The method comprises the following steps: (1) mixing the reactive diluent, the photoinitiator, and optionally the co-initiator under light shielding conditions until the initiator is completely dissolved to obtain a mixed solution; (2) adding the polyester modified epoxy acrylate, the aliphatic polyurethane acrylate prepolymer, and the toughening agent to the mixed solution under light shielding conditions and stirring to obtain a photocuring resin composition.

8. The production method according to claim 7, wherein In step (2), the stirring conditions include a stirring temperature of 40-60℃ and a stirring time of 1-2h.

9. A photocurable resin material, characterized by, The photocuring resin material is prepared from the photocuring resin composition according to any one of claims 1-6.

10. Use of the photocurable resin composition according to any one of claims 1 to 6 or the photocurable resin material according to claim 9 in the field of photocurable rapid prototyping.