Liquid resin and preparation method thereof, and temperature-sensitive resin and preparation method thereof

Abstract

The invention relates to the technical field of resin, in particular to liquid resin and a preparation method thereof, and temperature-sensitive resin and a preparation method thereof. The liquid resin comprises 35-99% of a resin matrix, 1-40% of a temperature-sensitive raw material, 0-60% of a filler, 0-3% of a color-changing indicator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator, 0-3% of a color fading activator and 0-3% of a color fading activator. The use amount of the photoinitiator accounts for 0.5-3% of the total mass of the raw materials, and the use amount of the auxiliary agent accounts for 0.3-3% of the total mass of the raw materials. The resin has high transparency after being photo-cured, can also realize curing discoloration so as to determine the curing state through the appearance color, can be subjected to temperature-sensitive soft shaping after being cured, has good mechanical properties and extremely high fluidity, can be prepared through a simple process, and has no pungent smell and no cytotoxicity.

Description

Technical Field

[0001] The present invention relates to the field of resin technology, and in particular to a liquid resin and a preparation method thereof, a temperature-sensitive resin and a preparation method thereof. Background Art

[0002] Photocuring technology is a new material processing and molding method that has emerged in recent years. This technology can produce parts with diverse shapes and appearances and personalized features, greatly simplifying the production process of products. At present, photocuring resins are generally prepared using oligomers such as polyacrylic resins, epoxy acrylic resins, and polyurethane acrylic resins as raw materials, active monomers such as acrylates and vinyl ethers, cationic, free radical, free radical / cationic hybrid photoinitiators, and other additives.

[0003] For example, CN101665552A discloses a 3D printing photosensitive resin prepared from six different components, including 2-bis(2-mercaptoethylthio)-3-mercaptopropane, isocyanates, A-methyl methacrylate, tetrabromobisphenol A 2-hydroxy-3-phenoxy propyl acrylate, and styrene compounds. However, due to the complex structure and composition, it contains styrenes with strong odors and tetrabromobisphenol A compounds with greater hazards, and the preparation process is complicated and the cost is high. Therefore, it cannot be used for large-scale industrial production. In addition, the resin has many additives, the required preparation time is long, and there is a lack of detailed parameters in the printing process of 3D printing, which leads to inconvenience in application.

[0004] It can be seen that the transparency of traditional photocurable resin decreases after curing, which affects the user's use, observation, and judgment. Moreover, the resin is fixed after photocuring and can no longer be softened and shaped.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a liquid resin and a preparation method thereof, a temperature-sensitive resin and a preparation method thereof. The embodiment of the present invention provides a liquid resin, which has high transparency after light curing, can also achieve curing color change, so that the curing state can be determined by the appearance color, and can be softened and shaped by temperature after curing, has good mechanical properties and extremely high fluidity, can be prepared by a simple process, has no irritating odor, and has no cytotoxicity.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides a liquid resin, the raw materials of which include a resin matrix, a temperature-sensitive raw material, a filler, a color change indicator, a fading activator, a photoinitiator and an auxiliary agent.

[0009] The amount of the resin matrix accounts for 35-99% of the total mass of the raw materials, the amount of the temperature-sensitive raw materials accounts for 1-40% of the total mass of the raw materials, the amount of the filler accounts for 0-60% of the total mass of the raw materials, the amount of the color change indicator accounts for 0-3% of the total mass of the raw materials, the amount of the fading activator accounts for 0-3% of the total mass of the raw materials, the amount of the photoinitiator accounts for 0.5-3% of the total mass of the raw materials, and the amount of the auxiliary agent accounts for 0.3-3% of the total mass of the raw materials.

[0010] In an optional embodiment, the amount of the resin matrix accounts for 60-99% of the total mass of the raw materials;

[0011] Preferably, the amount of the temperature-sensitive raw material accounts for 20-30% of the total mass of the raw material;

[0012] Preferably, the amount of the filler is 0% or 20-30% of the total mass of the raw material;

[0013] Preferably, the amount of the color change indicator is 0.001-0.5% of the total mass of the raw material;

[0014] Preferably, the amount of the fading activator is 0.001-0.8% of the total mass of the raw material;

[0015] Preferably, the amount of the photoinitiator is 1-2% of the total mass of the raw materials;

[0016] Preferably, the amount of the auxiliary agent used accounts for 0.3-1% of the total mass of the raw material.

[0017] In an optional embodiment, the resin matrix includes a resin monomer and a reactive diluent monomer;

[0018] Preferably, the mass ratio of the resin monomer to the reactive diluent monomer is 1:1 to 8:1.

[0019] In an optional embodiment, the resin monomer is selected from at least one of acrylic resin, epoxy resin and polyether resin;

[0020] Preferably, the resin monomer is selected from at least one of bisphenol A-glycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, dimethacrylate urethane and aromatic dimethacrylate diisocyanate.

[0021] In an optional embodiment, the reactive diluent monomer is selected from any one of a monofunctional acrylic resin, a difunctional acrylic resin and a multifunctional acrylic resin;

[0022] Preferably, the reactive diluent monomer is selected from at least one of triethylene glycol dimethacrylate, 1,12-dodecanediol dimethacrylate, hydroxyethyl methacrylate, N-acryloylmorpholine, cyclic trimethylolpropane formal acrylate and hydroxybutyl acrylate.

[0023] In an optional embodiment, the temperature-sensitive raw material is selected from at least one of a polyether compound or an acrylate compound having a Tg of no more than 20°C and a heat deformation temperature after curing of no more than 45°C;

[0024] Preferably, the temperature-sensitive raw material is selected from any one or at least two of AgiSyn 703, EBECRYL 880, HC-P02, BASF Ultracur3DEL150 and 1,6-hexanediol diacrylate.

[0025] In an optional embodiment, the auxiliary agent includes any one or at least two of a UV protectant, an antioxidant, an inhibitor, a defoamer and a dispersant;

[0026] Preferably, the color change indicator is selected from any one or at least two of erythrosine B, eosin yellow, eosin Y, ethyl eosin, methylene violet, capsanthin, eosin blue, acid red 94, methylene blue and ultramarine;

[0027] Preferably, the fading activator is selected from any one or at least two of diphenyl iodonium hexafluorophosphate, bis(4-tert-butylbenzene) iodonium hexafluorophosphate, 4,4"-ditolyl iodonium hexafluorophosphate, diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and triarylsulfonium salts;

[0028] Preferably, the UV protective agent is selected from any one or at least two of UV1, UV9, UV-P and UVK-YK05;

[0029] Preferably, the antioxidant is selected from any one or at least two of antioxidants 168, 300, 626, 1010, 1076, 1098, 2020, 330DW, PDP, V-220, V-76P, BHA, BHT, PG and HQ.

[0030] In a second aspect, the present invention provides a method for preparing the liquid resin described in the aforementioned embodiment, comprising mixing and stirring a resin matrix, a temperature-sensitive raw material, a filler, a color change indicator, a fading activator, a photoinitiator and an auxiliary agent;

[0031] Preferably, the components other than the defoamer and the dispersant are mixed and stirred, and the stirring conditions include: a time of 4-24 hours, a rotation speed of 500-2000 rpm, and an ultrasonic time of 5-30 minutes;

[0032] Then, a defoamer and a dispersant are added and stirred in the dark. The stirring conditions include: 5-60 minutes, a rotation speed of 100-1000 rpm, and an ultrasonic time of 5-30 minutes.

[0033] In a third aspect, the present invention provides a temperature-sensitive resin, which is prepared by the liquid resin described in the aforementioned embodiment.

[0034] In a fourth aspect, the present invention provides a method for preparing the temperature-sensitive resin described in the aforementioned embodiment, comprising photocuring the liquid resin described in the aforementioned embodiment;

[0035] Preferably, the wavelength of the light source for photocuring is 360-420 nm.

[0036] The present invention has the following beneficial effects: the embodiments of the present invention select a specific resin matrix, temperature-sensitive raw materials, etc., so that the liquid resin formed after light curing has the advantages of temperature-sensitive softening properties, low viscosity, high strength, high transparency, etc., and can also achieve curing color change, so that the curing state can be determined by the appearance color. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0038] Figure 1 A schematic diagram of the fluidity of the liquid resin provided in Example 1 of the present invention;

[0039] Figure 2 Pictures of liquid resin and temperature-sensitive resin provided in Example 3 of the present invention;

[0040] Figure 3 Pictures of liquid resin and temperature-sensitive resin provided in Example 1 of the present invention;

[0041] Figure 4 This is a picture of the liquid resin and the cured resin provided for Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention will be described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments used is not specified, they are all conventional products that can be purchased commercially.

[0043] The embodiment of the present invention provides a liquid resin, the raw materials of which include a resin matrix, a temperature-sensitive raw material, a filler, a color change indicator, a fading activator, a photoinitiator and an auxiliary agent.

[0044] Among them, the amount of resin matrix accounts for 35-99% of the total mass of the raw materials, for example, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90% and 99%, etc., any value between 35-99% or a range value between any two values, for example, preferably 60-99%.

[0045] The resin matrix includes a resin monomer and a reactive diluent monomer, wherein the mass ratio of the resin monomer to the reactive diluent monomer is 1:1 to 8:1, such as 1:1, 2:2, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, and any other value between 1:1 and 8:1.

[0046] Furthermore, the resin monomer is selected from at least one of acrylate resins, epoxy resins and polyether resins; for example, including but not limited to at least one of bisphenol A-glycidyl dimethacrylate (bisGMA), ethoxylated bisphenol A dimethacrylate (bisEMA), urethane dimethacrylate (UDMA), and aromatic dimethacrylate diisocyanate (AUDMA).

[0047] The reactive diluent monomer is selected from any one of monofunctional acrylic resins, difunctional acrylic resins and multifunctional acrylic resins; for example, including but not limited to at least one of triethylene glycol dimethacrylate (TEGDMA), 1,12-dodecanediol dimethacrylate (DDDMA), hydroxyethyl methacrylate (HEMA), N-acryloylmorpholine (ACMO), cyclic trimethylolpropane formal acrylate (CTFA), and hydroxybutyl acrylate (4-HBA).

[0048] The amount of the temperature-sensitive raw material accounts for 1-40% of the total mass of the raw material, such as 1%, 10%, 20%, 30% and 40%, any value between 1-40% or a range of any values, such as preferably 20-30%.

[0049] The temperature-sensitive raw material is selected from at least one of polyether compounds or acrylate compounds with a Tg of no more than 20°C and a heat deformation temperature of no more than 45°C after curing; for example, including but not limited to any one or at least two of AgiSyn703, EBECRYL 880, HC-P02, BASF Ultracur3D EL150 and 1,6-hexanediol diacrylate.

[0050] The amount of the filler is 0-60% of the total mass of the raw materials, that is, filler may be absent or may be present. If filler is present, the amount may be any value between 0-60%, such as 1%, 10%, 20%, 30%, 40%, 50% and 60%, or a range value between any values, for example, preferably 0% or 20-30%.

[0051] The filler can be an inorganic filler, for example, including but not limited to glass powder, strontium glass powder, silicon dioxide, zirconium oxide, aluminum oxide, hydroxyapatite, β-tricalcium phosphate, zinc oxide, titanium oxide or one or more, with an average particle size ranging from 0.01 to 10 μm, and preferably surface treated with a silane coupling agent.

[0052] The amount of the color changing indicator is 0-3% of the total mass of the raw material, that is, the color changing indicator may be used or not, for example, the amount of the color changing indicator is 1%, 1.5%, 2%, 2.5% and 3%, any value between 0-3% or a range value between any two values.

[0053] The color change indicator is selected from any one or at least two of erythrosine B, eosin yellow, eosin Y, ethyl eosin, methylene violet, capsanthin, eosin blue, acid red 94, methylene blue and ultramarine.

[0054] The amount of the fading activator used is 0-3% of the total mass of the raw material, that is, the fading activator may be used or not, for example, the amount of the fading activator used is 1%, 1.5%, 2%, 2.5% and 3%, any value between 0-3% or a range value between any two values.

[0055] The color change indicator and the fading activator are combined to make the liquid resin have color before curing, and transparent and colorless after curing, and the transparency is high. By making the color of the liquid resin change before and after curing, the operator can judge the curing status of the liquid resin only by observing the color change, which can further reduce the difficulty of the operator's operation.

[0056] Furthermore, the amount of the photoinitiator is 0.5-3% of the total mass of the raw material, for example, 0.5%, 1%, 1.5%, 2.5% and 3%, etc., any value between 0.5-3% or a range between any two values.

[0057] The photoinitiator is selected from existing photoinitiators, such as, but not limited to, one or more of TPO (diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide), TPO-L, TMO ((2,4,6-trimethylbenzoyl)di(p-tolyl)phosphine oxide), CQ (camphorquinone), photoinitiator 819 (phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide), and photoinitiator 184 (1-hydroxycyclohexyl phenyl ketone).

[0058] The dosage of the auxiliary agent accounts for 0.3-3% of the total mass of the raw material, for example, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5% and 3%, etc., any value between 0.3-3% or a range value between any two values.

[0059] Specifically, the auxiliary agent can be selected from any one or at least two of an ultraviolet protective agent, an antioxidant, an inhibitor, a defoaming agent and a dispersant.

[0060] Specifically, the amount of the ultraviolet protective agent is 0.0001%-0.3%. The ultraviolet protective agent is selected from any one or at least two of UV1, UV9, UV-P and UVK-YK05.

[0061] The dosage of the antioxidant is 0.0001%-0.3%. The antioxidant is selected from any one or at least two of antioxidants 168, 300, 626, 1010, 1076, 1098, 2020, 330DW, PDP, V-220, V-76P, BHA, BHT, PG and HQ.

[0062] The combination of UV protectants and antioxidants can reduce or prevent yellowing of the cured resin and further improve the performance of the cured resin.

[0063] The dosage of the polymerization inhibitor is 0.0001%-0.3%. The polymerization inhibitor includes but is not limited to one or more of polymerization inhibitors 510, 525, 701, MMA, 90SD, tert-butyl hydroquinone (MTBHQ), and p-hydroxyanisole (MEHQ).

[0064] The dosage of the defoamer is 0.0001%-0.3%. The defoamer includes but is not limited to one or more of BYK-A530, BYK-066N, and MY-983.

[0065] The dosage of the dispersant is 0-0.3%. The dispersant includes but is not limited to one or more of MY-3031, byk-111, and DCA-9560.

[0066] The embodiment of the present invention selects the above materials and limits the amount of each material, so that the formed liquid resin is colored before curing, and colorless and transparent after curing, and has high transparency. At the same time, the cured resin has a temperature-sensitive property. Specifically, the cured resin will soften after heating, and then can be reshaped, and can be solidified again after cooling.

[0067] In a second aspect, the present invention provides a method for preparing the liquid resin described in the aforementioned embodiment, comprising:

[0068] The components except the defoamer and the dispersant are mixed and stirred, and the stirring conditions at this time include: time for 4-24h, rotation speed for 500-2000rpm, and ultrasonic time for 5-30min; then the defoamer and the dispersant are added and stirred in the dark, and the stirring conditions at this time include: 5-60min, rotation speed for 100-1000rpm, and ultrasonic time for 5-30min.

[0069] In a third aspect, the present invention provides a temperature-sensitive resin, which is prepared by the liquid resin described in the above embodiment. Specifically, the temperature-sensitive resin is obtained by curing the liquid resin.

[0070] Among them, the wavelength of the light source for photocuring is 360-420nm.

[0071] The features and performance of the present invention are further described in detail below in conjunction with the embodiments.

[0072] Example 1

[0073] The embodiment of the present invention provides a liquid resin, the components of which are as follows:

[0074] 38 parts of bisEMA; 30 parts of UDMA; 10 parts of TEGDMA; 20 parts of AgiSyn 703; 1 part of TPO; 0.02 parts of UVK-YK05; 0.1 parts of antioxidant 168; 0.5 parts of inhibitor 510; 0.01 parts of ultramarine blue; 0.2 parts of diphenyl iodonium hexafluorophosphate; and 0.1 parts of BYK-A530.

[0075] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0076] The components except the defoamer and dispersant were added into the reaction container in sequence, stirred in the dark for 6 hours, at a speed of 1000 rpm, and ultrasonically vibrated for 10 minutes. After adding the defoamer and dispersant, stirred in the dark for 30 minutes, at a speed of 300 rpm, and ultrasonically vibrated for 10 minutes. Vacuum stirring was performed for 10 minutes, and a uniformly mixed resin was obtained at 20 rpm.

[0077] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0078] The liquid resin is cured by using a light source with a wavelength of 405 nm.

[0079] Example 2

[0080] The embodiment of the present invention provides a liquid resin, the components of which are as follows:

[0081] 20 parts of bisEMA; 40 parts of UDMA; 10 parts of HEMA; 10 parts of HC-P02; 17 parts of HDDA; 2 parts of TPO; 0.5 parts of photoinitiator 184; 0.1 parts of BHT; 0.3 parts of MMA; 0.1 parts of UV1; 0.08 parts of UVK-YK05; 0.05 parts of ultramarine; 0.1 parts of inhibitor 701; 0.2 parts of byk-111; and 0.2 parts of MY-983.

[0082] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0083] The components except the defoamer and dispersant were added into the reaction container in sequence, stirred in the dark for 24 hours, at a speed of 2000 rpm, and ultrasonically vibrated for 10 minutes. After adding the defoamer and dispersant, stirred in the dark for 10 minutes, at a speed of 400 rpm, ultrasonically vibrated for 5 minutes, and vacuum stirred for 5 minutes at a speed of 50 rpm to obtain a uniformly mixed resin.

[0084] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0085] The liquid resin is cured by using a light source with a wavelength of 395 nm.

[0086] Example 3

[0087] The embodiment of the present invention provides a liquid resin, the ingredients of which are as follows: 70 parts of bisEMA; 10 parts of UDMA; 10 parts of CTFA; 8.5 parts of Ultracur3D EL150; 1.5 parts of TMO; 0.3 parts of antioxidant 1010; 0.1 parts of MEHQ; 0.2 parts of UV-P; 0.001 parts of methylene blue; 0.3 parts of inhibitor 510; 0.05 parts of MY-983; and 0.05 parts of 4,4'-dimethylphenyl iodide hexafluorophosphate.

[0088] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0089] The components except the defoamer and dispersant were added into the reaction container in sequence, stirred in the dark for 4 hours, at a speed of 1500 rpm, and ultrasonically vibrated for 10 minutes. After adding the defoamer and dispersant, stirred in the dark for 30 minutes, at a speed of 500 rpm, ultrasonically vibrated for 5 minutes, and vacuum stirred for 5 minutes at a speed of 20 rpm to obtain a uniformly mixed resin.

[0090] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0091] The liquid resin is cured by using a light source with a wavelength of 385 nm.

[0092] Example 4

[0093] The embodiment of the present invention provides a liquid resin, the ingredients of which are as follows: 20 parts of bisEMA, 29 parts of UDMA, 10 parts of DDDMA, 37 parts of HDDA, 3 parts of TPO-L, 0.05 parts of V-220, 0.2 parts of MTBHQ, 0.005 parts of eosin blue, 0.5 parts of inhibitor 701, and 0.5 parts of BYK-066N.

[0094] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0095] The components except the defoamer and dispersant were added into the reaction container in sequence, stirred in the dark for 6 hours, at a speed of 600 rpm, and ultrasonically vibrated for 5 minutes. After adding the defoamer and dispersant, stirred in the dark for 5 minutes, at a speed of 1000 rpm, ultrasonically vibrated for 5 minutes, and vacuum stirred for 5 minutes at a speed of 20 rpm to obtain a uniformly mixed resin.

[0096] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0097] The liquid resin is cured by using a light source with a wavelength of 405 nm.

[0098] Example 5

[0099] The embodiment of the present invention provides a liquid resin, the components of which are as follows:

[0100] 30 parts of bisEMA; 5 parts of bisGMA; 20 parts of UDMA; 10 parts of DDDMA; 33 parts of HDDA; 1 part of TPO-L; 0.5 parts of photoinitiator 819; 0.5 parts of 330DW; 0.02 parts of inhibitor 701; 0.2 parts of UV1; 0.005 parts of eosin blue; 0.5 parts of inhibitor 701; 0.1 parts of bis(4-tert-butylbenzene)iodonium hexafluorophosphate.

[0101] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0102] The components other than the defoamer and dispersant were sequentially added to the reaction vessel and stirred for 24 hours in the dark, at a speed of 500 rpm, and ultrasonically vibrated for 20 minutes. After adding the defoamer and dispersant, they were stirred for 10 minutes in the dark, at a speed of 200 rpm, ultrasonically vibrated for 5 minutes, and vacuum stirred for 5 minutes at a speed of 50 rpm to obtain a uniformly mixed resin.

[0103] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0104] The liquid resin is cured by using a light source with a wavelength of 365 nm.

[0105] Example 6

[0106] The embodiment of the present invention provides a liquid resin, whose ingredients are as follows: 50 parts of bisEMA; 15 parts of UDMA; 10 parts of HEMA; 2 parts of HDDA; 2 parts of TPO; 0.5 parts of photoinitiator 184; 0.1 parts of BHT; 0.3 parts of MMA; 0.1 parts of UV1; 0.08 parts of UVK-YK05; 20 parts of barium glass powder; 0.1 parts of inhibitor 701; 0.2 parts of byk-111; 0.2 parts of MY-983; 0.5 parts of DCA-9560.

[0107] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0108] The components except the defoamer and dispersant were added into the reaction container in sequence, stirred in the dark for 24 hours, at a speed of 1000 rpm, and ultrasonically vibrated for 30 minutes. After adding the defoamer and dispersant, stirred in the dark for 30 minutes, at a speed of 500 rpm, ultrasonically vibrated for 30 minutes, and vacuum stirred for 30 minutes, at a speed of 100 rpm to obtain a uniformly mixed resin.

[0109] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0110] The liquid resin is cured by using a light source with a wavelength of 405 nm.

[0111] Example 7

[0112] The embodiment of the present invention provides a liquid resin, whose ingredients are as follows: 40 parts of bisEMA; 5 parts of UDMA; 10 parts of EBECRYL880; 3 parts of HEMA; 10 parts of HDDA; 1 part of TPO; 0.5 parts of photoinitiator 184; 0.1 parts of BHT; 0.3 parts of MMA; UV10.1 parts; UVK-YK05 0.08 parts; 40 parts of zirconium oxide; 0.1 parts of inhibitor 701; 0.2 parts of byk-111; 0.2 parts of MY-983; 0.5 parts of DCA-9560.

[0113] The embodiment of the present invention also provides a method for preparing the liquid resin, comprising:

[0114] The components except the defoamer and dispersant were added into the reaction container in sequence, stirred in the dark for 24 hours, at a speed of 2000 rpm, and ultrasonically vibrated for 30 minutes. After adding the defoamer and dispersant, stirred in the dark for 60 minutes, at a speed of 200 rpm, ultrasonically vibrated for 30 minutes, and vacuum stirred for 30 minutes at a speed of 20 rpm to obtain a uniformly mixed resin.

[0115] An embodiment of the present invention provides a method for preparing a temperature-sensitive resin, comprising:

[0116] The liquid resin is cured by using a light source with a wavelength of 405 nm.

[0117] Comparative Example 1: This comparative example provides a liquid resin, whose components are: 59 parts of bisEMA; 30 parts of UDMA; 10 parts of TEGDMA; and 1 part of TPO.

[0118] The above components were sequentially added into a reaction vessel and stirred for 6 hours in the dark, at a speed of 1000 rpm, ultrasonically vibrated for 10 minutes, and vacuum stirred for 10 minutes at 20 rpm to obtain a uniformly mixed resin. The liquid resin was cured using a light source with a wavelength of 405 nm to form a cured resin.

[0119] Test Example 1

[0120] The fluidity of the liquid resin of Example 1 was tested in the following manner: the liquid resin was slowly poured out from a container to observe its flow.

[0121] Results Figure 1 ,according to Figure 1 It can be seen that the resin has excellent fluidity. At the same time, the viscosity can refer to the viscosity test data provided in the test example of the present invention.

[0122] Test Example 2

[0123] The viscosity of the liquid resins of Examples 1 and 2 and the competitor's product was tested at 20° C. The viscosity method was as follows: the liquid resin was placed in a special container (sample container) of a viscometer and its viscosity was measured. The results are shown in Table 1.

[0124] Table 1 Viscosity results

[0125] Example Viscosity (mPa s) 1 593 2 641 A domestic competitor 899 A foreign competitor 740

[0126] It can be seen that the liquid value provided by the embodiment of the present invention has a lower viscosity, indicating that it has good fluidity.

[0127] Test Example 3

[0128] The temperature-sensitive resins of Examples 1 and 2 and the cured resin of Comparative Example 1 were heated to 45°C, and the bending strength and bending modulus of the temperature-sensitive resins were tested at 20°C, 45°C, and after being heated at 45°C and then cooled to 20°C. The detection method is as follows: the samples of the examples and the competitive products were respectively cured into corresponding test strips using corresponding molds and tested using a universal material testing machine.

[0129] The test results are shown in Table 2.

[0130] Table 2 Flexural strength and flexural modulus

[0131]

[0132] According to Table 2, the thermosensitive resin provided in the embodiment of the present invention has a thermosensitive property, and will become soft after being heated again, and can then be reshaped. Moreover, after being heated and cooled again, the relevant bending strength and bending modulus are not much different from the data of the initial curing.

[0133] Test Example 4

[0134] The MTT method was used to test the cell activity of the thermosensitive resins of Examples 1 and 2. Specifically, L929 cells were used to perform the test in accordance with GB / T 16886.5-2017, and the results are shown in Table 3.

[0135] Table 3 Cell activity

[0136]

[0137]

[0138] It can be seen from Table 3 that the temperature-sensitive resin provided in the embodiment of the present invention has no cytotoxicity and is harmless to the human body.

[0139] Test Example 5

[0140] The morphology of the liquid resins of Examples 1, 3 and Comparative Example 1 before and after curing was photographed. Figure 2-Figure 4 ,in, Figure 2 The left side of the figure shows the uncured liquid resin of Example 3. Figure 2 The right side in the middle shows the cured temperature-sensitive resin of Example 3. Figure 3 The left side of the figure shows the uncured liquid resin of Example 1. Figure 3 The right side of the middle diagram shows the cured temperature-sensitive resin of Example 1. Figure 4 The left side of the figure shows the uncured liquid resin of Comparative Example 1. Figure 4 The right side in the middle shows the solid resin of Comparative Example 1 after curing.

[0141] according to Figure 2 , Figure 3 and Figure 4 It can be seen that the color of the liquid resin provided by the embodiment of the present invention changes significantly before and after curing, which realizes visual judgment of the curing process, indicating that the operator can judge whether the resin is cured only by the naked eye, and the resin has high transparency, which expands the application range of the resin. However, by changing the formula of the liquid resin provided by the embodiment of the present invention, there is no obvious change in color before and after the liquid resin is cured, and it is impossible to judge whether it is completely cured from the color. This further illustrates that the liquid resin provided by the embodiment of the present invention has excellent effects.

[0142] Test Example 6

[0143] The liquid resins of Examples 1, 2, Comparative Example 1 and the competitor's product were respectively cured into discs with a diameter of 10 mm and a thickness of 2 mm, and the transmittance in the visible light range (400-700 nm) was tested using a UV-visible spectrophotometer.

[0144]

[0145] According to the above table, it can be seen that the temperature-sensitive resin provided by the embodiment of the present invention has good light transmittance, and the light transmittance remains unchanged even after reshaping.

[0146] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A liquid resin, characterized in that: Its raw materials include resin matrix, temperature-sensitive raw materials, fillers, color change indicators, fading activators, photoinitiators and additives; The amount of the resin matrix accounts for 35-99% of the total mass of the raw materials, the amount of the temperature-sensitive raw materials accounts for 1-40% of the total mass of the raw materials, the amount of the filler accounts for 0-60% of the total mass of the raw materials, the amount of the color change indicator accounts for 0-3% of the total mass of the raw materials, the amount of the fading activator accounts for 0-3% of the total mass of the raw materials, the amount of the photoinitiator accounts for 0.5-3% of the total mass of the raw materials, and the amount of the auxiliary agent accounts for 0.3-3% of the total mass of the raw materials.

2. The liquid resin according to claim 1, characterized in that The amount of the resin matrix accounts for 60-99% of the total mass of the raw materials; Preferably, the amount of the temperature-sensitive raw material accounts for 20-30% of the total mass of the raw material; Preferably, the amount of the filler is 0% or 20-30% of the total mass of the raw material; Preferably, the amount of the color change indicator is 0.001-0.5% of the total mass of the raw material; Preferably, the amount of the fading activator is 0.001-0.8% of the total mass of the raw material; Preferably, the amount of the photoinitiator is 1-2% of the total mass of the raw materials; Preferably, the amount of the auxiliary agent used accounts for 0.3-1% of the total mass of the raw material.

3. The liquid resin according to claim 1, characterized in that The resin matrix includes resin monomers and reactive diluent monomers; Preferably, the mass ratio of the resin monomer to the reactive diluent monomer is 1:1 to 8:

1.

4. The liquid resin according to claim 3, characterized in that The resin monomer is selected from at least one of acrylate resin, epoxy resin and polyether resin; Preferably, the resin monomer is selected from at least one of bisphenol A-glycidyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, dimethacrylate urethane and aromatic dimethacrylate diisocyanate.

5. The liquid resin according to claim 3, characterized in that: The reactive diluent monomer is selected from any one of monofunctional acrylic resin, bifunctional acrylic resin and multifunctional acrylic resin; Preferably, the reactive diluent monomer is selected from at least one of triethylene glycol dimethacrylate, 1,12-dodecanediol dimethacrylate, hydroxyethyl methacrylate, N-acryloylmorpholine, cyclic trimethylolpropane formal acrylate and hydroxybutyl acrylate.

6. The liquid resin according to claim 1 or 2, characterized in that: The temperature-sensitive raw material is selected from at least one of a polyether compound or an acrylic compound having a Tg of no more than 20°C and a thermal deformation temperature after curing of no more than 45°C; Preferably, the temperature-sensitive raw material is selected from any one or at least two of AgiSyn 703, EBECRYL 880, HC-P02, BASF Ultracur3DEL150 and 1,6-hexanediol diacrylate.

7. The liquid resin according to claim 1 or 2, characterized in that: The auxiliary agent includes any one or at least two of an ultraviolet protective agent, an antioxidant, an inhibitor, a defoaming agent and a dispersant; Preferably, the color change indicator is selected from any one or at least two of erythrosine B, eosin yellow, eosin Y, ethyl eosin, methylene violet, capsanthin, eosin blue, acid red 94, methylene blue and ultramarine; Preferably, the fading activator is selected from any one or at least two of diphenyl iodonium hexafluorophosphate, bis(4-tert-butylbenzene) iodonium hexafluorophosphate, 4,4'-ditolyl iodonium hexafluorophosphate, diphenyl-(4-phenylthio)phenylsulfonium hexafluorophosphate and triarylsulfonium salts; Preferably, the UV protective agent is selected from any one or at least two of UV1, UV9, UV-P and UVK-YK05; Preferably, the antioxidant is selected from any one or at least two of antioxidants 168, 300, 626, 1010, 1076, 1098, 2020, 330DW, PDP, V-220, V-76P, BHA, BHT, PG and HQ.

8. A method for preparing the liquid resin according to claim 1, characterized in that: Mix and stir the resin matrix, the temperature-sensitive raw material, the filler, the color change indicator, the fading activator, the photoinitiator and the auxiliary agent; Preferably, the components other than the defoamer and the dispersant are mixed and stirred, and the stirring conditions include: a time of 4-24 hours, a rotation speed of 500-2000 rpm, and an ultrasonic time of 5-30 minutes; Then, a defoamer and a dispersant are added and stirred in the dark. The stirring conditions include: 5-60 minutes, a rotation speed of 100-1000 rpm, and an ultrasonic time of 5-30 minutes.

9. A temperature-sensitive resin, characterized in that: The liquid resin is prepared by the liquid resin described in claim 1.

10. A method for preparing the temperature-sensitive resin according to claim 9, characterized in that: The method comprises photocuring the liquid resin according to claim 1; Preferably, the wavelength of the light source for photocuring is 360-420 nm.

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