Aminomethacrylate monomers, their preparation and use

Abstract

The application relates to the technical field of photosensitive resin, in particular to an amine methyl acrylate monomer as well as a preparation method and application thereof. The amine methyl acrylate monomer has the general structure shown in the following formula I: wherein n is an integer selected from 1-6. The amine methyl acrylate monomer has a low saturated vapor pressure and almost no irritating odor at a daily use temperature; the monomer has a flexible ethoxy (-CH2-CH2-O) structure, a low molecular chain rotation potential barrier, and improved molecular chain movement ability, and has good low-temperature toughness.

Description

Technical Field

[0001] This invention relates to the field of photosensitive resin technology, and in particular to an aminomethacrylate monomer, its preparation method, and its application. Background Technology

[0002] Aminomethacrylate monomers are a class of organic compounds containing amino and methacrylate groups, with typical examples including tert-butylaminopropyl methacrylate (TBAPMA), tert-butylaminobutyl methacrylate, and tert-butylaminoethyl methacrylate (TBAEMA). These compounds can serve as thermally reversible blocking agents for isocyanate prepolymers, demonstrating significant application value in the field of photocurable materials.

[0003] However, the industrial application of these aminomethacrylate monomers currently faces significant challenges. Among them, tert-butylaminopropyl methacrylate and tert-butylaminobutyl methacrylate monomers have not yet achieved large-scale production due to their complex synthetic routes and demanding reaction conditions. While tert-butylaminoethyl methacrylate has been industrialized, its volatility and strong irritant properties mean that materials prepared from it retain a pronounced amine odor, severely limiting its practical application in the field of photocurable materials.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The purpose of this invention is to provide aminomethacrylate monomers, their preparation methods, and applications. This invention provides a novel aminomethacrylate monomer with low saturated vapor pressure and virtually no irritating odor at normal operating temperatures; furthermore, photocurable products obtained using this monomer exhibit good low-temperature toughness, low volume shrinkage, and low skin irritation.

[0006] To achieve the above-mentioned objectives of the present invention, a first aspect of the present invention provides an aminomethacrylate monomer having the general structural formula shown in Formula I:

[0007] ;

[0008] Where n is selected from integers between 1 and 6.

[0009] A second aspect of the present invention provides a method for preparing aminomethacrylate monomers, comprising the following steps:

[0010] Methyl methacrylate undergoes transesterification with a substance represented by Formula II below;

[0011] ;

[0012] Where n is selected from integers between 1 and 6.

[0013] Furthermore, in the transesterification reaction, the molar ratio of the methyl methacrylate to the substance represented by the structure of Formula II is (2-4):1.

[0014] Furthermore, the temperature of the transesterification reaction is 90–120°C; the time of the transesterification reaction is 1–3 hours.

[0015] Furthermore, the transesterification reaction is carried out under the catalysis of a catalyst, which comprises a solid base.

[0016] Furthermore, the transesterification reaction is carried out in the presence of a polymerization inhibitor.

[0017] Furthermore, the transesterification system also includes an antioxidant.

[0018] Furthermore, after the transesterification reaction, the process further includes: performing solid-liquid separation on the material after the transesterification reaction, collecting the liquid phase, and purifying it to obtain the product.

[0019] A third aspect of the present invention provides a composition for polyurethane acrylic resin, comprising at least one of the aminomethacrylate monomers as described in the first aspect of the present invention and a terminal isocyanate prepolymer; wherein the molar ratio of the aminomethacrylate monomer to the NCO group in the terminal isocyanate prepolymer is (1 to 1.05):1.

[0020] Furthermore, the aminomethacrylate monomer includes any one of the following structures:

[0021] , , , , , .

[0022] Furthermore, the raw materials for preparing the terminal isocyanate prepolymer include polymeric polyols and polyisocyanates.

[0023] Furthermore, the polymeric polyol includes at least one of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol.

[0024] Furthermore, the polymerizable monomers of the polyester polyol include, optionally, a diol having 2 to 10 carbon atoms and an optional dicarboxylic acid having 4 to 12 carbon atoms.

[0025] Furthermore, the polyether polyol includes at least one of polytetrahydrofuran polyol, polyethylene oxide polyol, polypropylene oxide ether polyol, and polyethylene oxide-propylene oxide ether polyol.

[0026] Furthermore, the number-average molecular weight of the polymer polyol is 1000–3000 g / mol.

[0027] Furthermore, the functionality of the polymer polyol is 2 to 3.

[0028] Further, the polyisocyanate includes at least one of toluene diisocyanate, terephthalic diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0029] Furthermore, the molar ratio of the polymeric polyol to the polyisocyanate is 1:(2 to 2.1).

[0030] Furthermore, the NCO content in the terminal isocyanate prepolymer is 2wt% to 6wt%.

[0031] A fourth aspect of the present invention provides a polyurethane acrylic resin prepared from a composition of polyurethane acrylic resin as described in the third aspect of the present invention.

[0032] Furthermore, the polyurethane acrylic resin has the following terminal groups:

[0033] .

[0034] Furthermore, the molecular weight of the polyurethane acrylic resin is 1500–6200 g / mol.

[0035] Furthermore, the preparation of the polyurethane acrylic resin includes reacting a mixture of terminal isocyanate prepolymer and aminomethacrylate monomer at 50-60°C.

[0036] A fifth aspect of the present invention provides a composition for photosensitive resin, comprising the polyurethane acrylic resin as described in the fourth aspect of the present invention.

[0037] Furthermore, it also includes at least one of reactive diluents, photoinitiators, curing agents, thermal initiators, and defoamers.

[0038] Furthermore, the amount of the reactive diluent is 10wt% to 50wt% of the polyurethane acrylic resin.

[0039] Furthermore, the reactive diluent includes at least one of isooctyl methacrylate, ethoxyethoxyethyl methacrylate, triethylene glycol dimethacrylate, dodecyl methacrylate, and polyethylene glycol dimethacrylate.

[0040] Furthermore, the amount of photoinitiator is 0.3wt% to 3wt% of the polyurethane acrylic resin.

[0041] Furthermore, the photoinitiator includes at least one of photoinitiator TPO, photoinitiator 1173, photoinitiator 184, photoinitiator 819, and photoinitiator TMO.

[0042] Furthermore, the amount of the curing agent is 4wt% to 10wt% of the polyurethane acrylic resin.

[0043] Further, the curing agent includes at least one selected from 3,3-dimethyl-4,4-diaminodicyclohexylmethane, 4,4-diaminodicyclohexylmethane, 1,4-cyclohexanediamine, hexanediamine, octanediamine, and decanediamine.

[0044] Furthermore, the amount of the defoamer is 0.01wt% to 0.1wt% of the polyurethane acrylic resin.

[0045] Furthermore, the thermal initiator includes at least one of azo thermal initiators and peroxide thermal initiators, such as at least one of azobisisovalerate, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl peroxide, and dilauryl peroxide.

[0046] Furthermore, the amount of the thermal initiator is 0.1wt% to 1wt% of the polyurethane acrylic resin.

[0047] A sixth aspect of the present invention provides a photosensitive resin prepared from a composition of photosensitive resin as described in the fifth aspect of the present invention.

[0048] Furthermore, the glass transition temperature of the photosensitive resin is -40 to -10°C.

[0049] Furthermore, the volume shrinkage rate of the photosensitive resin is 2% to 6%.

[0050] The seventh aspect of the present invention provides the use of aminomethacrylate monomers as described in the first aspect of the present invention, compositions for polyurethane acrylic resins as described in the third aspect of the present invention, polyurethane acrylic resins as described in the fourth aspect of the present invention, compositions for photosensitive resins as described in the fifth aspect of the present invention, and photosensitive resins as described in the sixth aspect of the present invention in photocurable coatings, photocurable inks, or 3D printing materials.

[0051] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0052] (1) The aminomethacrylate monomers of the present invention have low saturated vapor pressure and almost no irritating odor at normal operating temperature; and the monomers of the present invention have a flexible ethoxy (-CH2-CH2-O) structure, low molecular chain rotation barrier, improved molecular chain mobility, and good low temperature toughness.

[0053] (2) When the aminomethacrylate monomers of the present invention are introduced into polyurethane acrylic resin, photosensitive resin and other materials, the carbon-carbon double bond is converted into a carbon-carbon single bond during photocuring, and the bond length is shortened; the ethoxy group, as a flexible long chain, has a large free volume, and compensates for part of the volume shrinkage through chain segment relaxation during the curing process, thereby reducing the shrinkage rate of the photocured product and improving the low temperature toughness of the photocured product.

[0054] (3) The ethoxy group in the aminomethacrylate monomers of the present invention is hydrophilic and can form hydrogen bonds with water in the environment, reducing the penetration and peeling of the skin lipid layer. Therefore, the skin irritation of the photocured products obtained by using the monomers of the present invention can be significantly reduced. Attached Figure Description

[0055] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0056] Figure 1 The mass spectrum of the aminomethacrylate monomer TBEEMA provided in the embodiments of the present invention;

[0057] Figure 2 The 1H NMR spectrum of the aminomethacrylate monomer TBEEMA provided in the embodiments of the present invention;

[0058] Figure 3 Infrared spectrum of TBEEMA, an aminomethacrylate monomer provided in an embodiment of the present invention. Detailed Implementation

[0059] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0060] The first aspect of this invention provides an aminomethacrylate monomer having the general structural formula shown in Formula I:

[0061] ;

[0062] Where n is selected from an integer between 1 and 6, specifically, n can be 1, 2, 3, 4, 5 or 6, and the corresponding structures of the monomers shown in Equation I are as follows:

[0063] (Named TBEEMA);

[0064] (Named TB(E)2EMA);

[0065] (Named TB(E)3EMA);

[0066] (Named TB(E)4EMA);

[0067] (Named TB(E)5EMA);

[0068] (Named TB(E)6EMA).

[0069] The aminomethacrylate monomers of the present invention have low saturated vapor pressure and almost no irritating odor at normal operating temperatures; moreover, the monomers of the present invention have a flexible ethoxy (-CH2-CH2-O) structure, with low molecular chain rotation barrier, improved molecular chain mobility, and good low-temperature toughness.

[0070] Furthermore, the ethoxy group in the aminomethacrylate monomers of the present invention is hydrophilic and can form hydrogen bonds with water in the environment, reducing the penetration and peeling effect on the skin lipid layer. Therefore, the skin irritation of the photocured products obtained using the monomers of the present invention can be significantly reduced.

[0071] A second aspect of the present invention provides a method for preparing aminomethacrylate monomers, comprising the following steps:

[0072] Methyl methacrylate undergoes transesterification with a substance represented by Formula II below;

[0073] ;

[0074] Where n is selected from an integer between 1 and 6, specifically, n can be 1, 2, 3, 4, 5 or 6, and the corresponding structures of the substances shown in Equation II are as follows:

[0075] , , , , , .

[0076] Transesterification is a relatively mature reaction, and the conditions for transesterification reactions in existing technologies can be referenced or adapted accordingly. In a preferred embodiment of the present invention, the molar ratio of methyl methacrylate to the substance represented by Formula II in the transesterification reaction is (2-4):1, specifically 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, or any combination thereof.

[0077] In a specific embodiment of the present invention, the temperature of the transesterification reaction is 90–120°C, specifically 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, or any combination thereof; the time of the transesterification reaction is 1–3 hours, specifically 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any combination thereof. The specific transesterification reaction time can be appropriately adjusted according to the reaction progress monitored by TLC.

[0078] In a specific embodiment of the present invention, the transesterification reaction is carried out under the catalysis of a catalyst; the catalyst includes a solid base. The solid base includes, but is not limited to, oxides or hydroxides of alkali metals or alkaline earth metals, such as calcium oxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide.

[0079] In a specific embodiment of the present invention, the amount of catalyst used is 0.2% to 2% of the mass of methyl methacrylate, for example, it can be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2% or any combination thereof.

[0080] In a specific embodiment of the present invention, the transesterification reaction is carried out in the presence of a polymerization inhibitor. Further, the polymerization inhibitor includes, but is not limited to, 4-hydroxy-2,2,6,6-tetramethylpiperidine nitroxide radical (polymerization inhibitor 701). Carrying the transesterification reaction in the presence of a polymerization inhibitor can prevent the self-polymerization of the reactant methyl methacrylate.

[0081] In a specific embodiment of the present invention, the amount of polymerization inhibitor is 0.05% to 0.1% of the mass of methyl methacrylate, for example, it can be 0.05%, 0.06%, 0.08%, 0.09%, 0.1% or any combination thereof.

[0082] In a specific embodiment of the present invention, the transesterification reaction system also includes antioxidants, including but not limited to antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 245, etc.

[0083] In a specific embodiment of the present invention, the amount of antioxidant used is 0.1% to 1% of the mass of methyl methacrylate, for example, it can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1% or any combination thereof.

[0084] In a specific embodiment of the present invention, after the transesterification reaction, the process further includes: solid-liquid separation of the material after the transesterification reaction, collection of the liquid phase, and purification treatment to obtain the product.

[0085] In a specific embodiment of the present invention, the purification process includes conventional distillation or column chromatography separation.

[0086] A third aspect of the present invention provides a composition for polyurethane acrylic resin, comprising at least one of the aminomethacrylate monomers as described in the first aspect of the present invention and a terminal isocyanate prepolymer; the molar ratio of the aminomethacrylate monomer to the NCO group in the terminal isocyanate prepolymer is (1 to 1.05):1.

[0087] The polyurethane acrylic resin composition of the present invention can be prepared by compounding aminomethyl acrylate monomers and terminal isocyanate prepolymers in a certain proportion, and the two are mixed and reacted with the -NH in the monomers by the terminal NCO groups. Introducing the structure of aminomethyl acrylate monomers into the resin can improve the low-temperature toughness of the polyurethane acrylic resin and reduce the shrinkage rate after photocuring.

[0088] In different embodiments, the molar ratio of the aminomethacrylate monomer to the NCO groups in the terminal isocyanate prepolymer can be 1:1, 1.01:1, 1.02:1, 1.03:1, 1.04:1, 1.05:1, or any combination thereof. By adjusting the ratio to meet the above conditions, the NCO in the terminal isocyanate prepolymer can react completely with the monomer when the two are compounded.

[0089] The mass percentage of NCO groups in the terminal isocyanate prepolymer can be determined according to the method described in HG / T 2409-2023 "Determination of Isocyanate Group Content in Polyurethane Prepolymer", and then converted into moles.

[0090] In a specific embodiment of the present invention, the aminomethacrylate monomer includes any one of the following structures:

[0091] (TBEEMA) (TB(E)2EMA), (TB(E)3EMA), (TB(E)4EMA), (TB(E)5EMA), (TB(E)6EMA).

[0092] In specific embodiments of the present invention, the above-mentioned structural substances are all prepared by mature reactions. For example, TBEEMA can be prepared directly by transesterification reaction of tert-butylaminoethoxyethanol with methyl methacrylate. Another example is the reaction of the products obtained by nucleophilic substitution reactions of activated triethylene glycol, activated tetraethylene glycol, activated pentaethylene glycol, activated hexaethylene glycol, or activated heptaethylene glycol with tert-butylamine with methyl methacrylate to obtain the above-mentioned monomers. Specifically, for example, TB(E)2EMA can be prepared by transesterification reaction of the product obtained by activating p-toluenesulfonyl chloride with triethylene glycol followed by nucleophilic substitution reaction with tert-butylamine.

[0093] In a specific embodiment of the present invention, the raw materials for preparing the terminal isocyanate prepolymer include polymeric polyols and polyisocyanates.

[0094] In a specific embodiment of the present invention, the polymeric polyol includes at least one of polyester polyol, polyether polyol, polycaprolactone polyol, and polycarbonate polyol.

[0095] In a specific embodiment of the present invention, the polymer monomers of the polyester polyol include, optionally, a diol having 2 to 10 carbon atoms and, optionally, a dicarboxylic acid having 4 to 12 carbon atoms.

[0096] In specific embodiments of the present invention, the diols having 2 to 10 carbon atoms include at least one of ethylene glycol, 1,4-butanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, neopentanediol, and 1,6-hexanediol; the dicarboxylic acids having 4 to 12 carbon atoms include at least one of succinic acid, glutaric acid, adipic acid, sebacic acid, and chlorophthalic acid.

[0097] In a specific embodiment of the present invention, the polyether polyol includes at least one of polytetrahydrofuran polyol, polyethylene oxide polyol, polypropylene oxide ether polyol, and polyethylene oxide-propylene oxide ether polyol.

[0098] In a specific embodiment of the present invention, the number average molecular weight of the polymer polyol is 1000 to 3000 g / mol, specifically it can be 1000 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2200 g / mol, 2500 g / mol, 2800 g / mol, 3000 g / mol or any combination thereof.

[0099] In a specific embodiment of the present invention, the functionality of the polymer polyol is 2 to 3.

[0100] In a specific embodiment of the present invention, the polyisocyanate includes at least one of toluene diisocyanate, terephthalic diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and isophorone diisocyanate.

[0101] In a specific embodiment of the present invention, the molar ratio of the polymeric polyol to the polyisocyanate is 1:(2-2.1), specifically within the range of 1:2, 1:2.02, 1:2.05, 1:2.08, 1:2.1, or any combination thereof. The molar ratio of the polymeric polyol to the polyisocyanate can be appropriately adjusted to obtain a terminal isocyanate prepolymer with the required NCO content.

[0102] In a specific embodiment of the present invention, the NCO content in the terminal isocyanate prepolymer is 2wt% to 6wt%, specifically it can be 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, or any combination thereof. Controlling the content of the terminal isocyanate prepolymer within the above range is more conducive to controlling the composition at a suitable operating viscosity and is also conducive to improving the strength and toughness of the cured product.

[0103] A fourth aspect of the present invention provides a polyurethane acrylic resin, which is prepared from a composition of the polyurethane acrylic resin as described in the third aspect of the present invention.

[0104] In a specific embodiment of the present invention, the polyurethane acrylic resin has the following terminal groups:

[0105] .

[0106] In a specific embodiment of the present invention, the molecular weight of the polyurethane acrylic resin is 1500 to 6200 g / mol, specifically within the range of 1500 g / mol, 1750 g / mol, 2000 g / mol, 2500 g / mol, 2900 g / mol, 3000 g / mol, 3500 g / mol, 3900 g / mol, 4500 g / mol, 5000 g / mol, 6000 g / mol, 6200 g / mol, or any combination thereof.

[0107] In a specific embodiment of the present invention, the preparation of polyurethane acrylic resin includes reacting a mixture of terminal isocyanate prepolymer and aminomethacrylate monomers at 50–60°C. Specifically, the reaction can be carried out within a range of 50°C, 52°C, 55°C, 58°C, 60°C, or any combination thereof. The reaction time can be adjusted based on the infrared spectrum detection results of the reaction system. The reaction is stopped when no NCO absorption peak is detected in the infrared spectrum. For example, the specific reaction time can be 1–2 hours, but is not limited to this.

[0108] A fifth aspect of the present invention provides a composition for photosensitive resins, comprising a polyurethane acrylic resin as described in the fourth aspect of the present invention.

[0109] When the polyurethane acrylate resin of the present invention is used in a photosensitive resin composition, it can achieve photocuring through a carbon-carbon double bond reaction during light treatment. At this time, due to the presence of aminomethyl acrylate monomers in the polyurethane acrylate resin, the low-temperature toughness after photocuring is improved and the volume shrinkage rate is reduced. Furthermore, the photocured product can be subjected to heat treatment to expose the NCO groups in the polyurethane acrylate resin, which can further react with the curing agent introduced into the photosensitive resin composition to form a three-dimensional cross-linked network, further improving the product performance.

[0110] In specific embodiments of the present invention, at least one of an active diluent, a photoinitiator, a curing agent, a thermal initiator, and a defoamer is also included.

[0111] In a specific embodiment of the present invention, the amount of reactive diluent is 10wt% to 50wt% of polyurethane acrylic resin, specifically 10wt%, 20wt%, 30wt%, 40wt%, 50wt% or any combination thereof.

[0112] In a specific embodiment of the present invention, the reactive diluent includes at least one selected from isooctyl methacrylate, ethoxyethoxyethyl methacrylate, triethylene glycol dimethacrylate, dodecyl methacrylate (LMA), and polyethylene glycol dimethacrylate. Polyethylene glycol dimethacrylate includes, but is not limited to, polyethylene glycol 400 dimethacrylate and polyethylene glycol 600 dimethacrylate. Specifically, the type and amount of reactive diluent are selected according to the properties of the polyurethane acrylic resin.

[0113] In a specific embodiment of the present invention, the amount of photoinitiator is 0.3wt% to 3wt% of the polyurethane acrylic resin, specifically it can be 0.3wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt% or any combination thereof.

[0114] In a specific embodiment of the present invention, the photoinitiator includes at least one of photoinitiator TPO, photoinitiator 1173, photoinitiator 184, photoinitiator 819, and photoinitiator TMO.

[0115] In a specific embodiment of the present invention, the amount of thermal initiator is 0.1 wt% to 1 wt% of the polyurethane acrylic resin. Specifically, it can be within the range of 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.5 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, or any combination thereof. The introduction of an appropriate amount of thermal initiator can initiate further reaction of any remaining unreacted acrylate monomers during the thermosetting stage, thereby reducing the volatile content.

[0116] In a specific embodiment of the present invention, the thermal initiator includes at least one of azo thermal initiators and peroxide thermal initiators, including but not limited to at least one of azobisisovalerate, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl peroxide, and dilauryl peroxide.

[0117] In a specific embodiment of the present invention, the amount of curing agent is 4wt% to 10wt% of polyurethane acrylic resin, specifically 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt% or any combination thereof.

[0118] In a specific embodiment of the present invention, the curing agent includes at least one selected from 3,3-dimethyl-4,4-diaminodicyclohexylmethane (DMDC), 4,4-diaminodicyclohexylmethane (PACM), 1,4-cyclohexanediamine, hexanediamine, octanediamine, and decanediamine.

[0119] In a specific embodiment of the present invention, the amount of defoamer used is 0.01wt% to 0.1wt% of the polyurethane acrylic resin, specifically within the range of 0.01wt%, 0.03wt%, 0.05wt%, 0.08wt%, 0.1wt%, or any combination thereof. The defoamer includes, but is not limited to, silicone-based defoamers.

[0120] In a specific embodiment of the present invention, the photosensitive resin composition does not include free diisocyanate monomers and / or reaction-blocked diisocyanate monomers. On the one hand, free diisocyanate monomers are easily volatile and toxic; on the other hand, free diisocyanate monomers or reaction-blocked diisocyanate monomers participate in the reaction with polyurethane acrylic resin, resulting in poor molecular chain segment regularity, which is not conducive to the separation of soft and hard microphases in polyurethane, leading to a decrease in material strength.

[0121] A sixth aspect of the present invention provides a photosensitive resin prepared from a composition of photosensitive resin as described in the fifth aspect of the present invention.

[0122] In a specific embodiment of the present invention, the glass transition temperature of the photosensitive resin is -40 to -10°C, specifically within the range of -40°C, -35°C, -30°C, -25°C, -20°C, -15°C, -10°C, or any combination thereof. The photosensitive resin obtained using the monomer of the present invention has a relatively low glass transition temperature, which can significantly improve the low-temperature toughness of the material.

[0123] In a specific embodiment of the present invention, the volume shrinkage rate of the photosensitive resin is 2% to 6%, for example, it can be a range of 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, or any combination thereof. The volume shrinkage rate is calculated as follows: the density of the composition used to prepare the photosensitive resin is ρ1, and the density of the photosensitive resin obtained using the composition is ρ2; the volume shrinkage rate is calculated according to (ρ2-ρ1) / ρ1×100%.

[0124] In this invention, when preparing the photosensitive resin using a photosensitive resin composition, it undergoes further thermal curing after photocuring. The thermal curing conditions include, but are not limited to, treatment at 100–120°C for 1–4 hours.

[0125] The seventh aspect of the present invention provides the application of aminomethacrylate monomers as described in the first aspect of the present invention, compositions for polyurethane acrylic resins as described in the third aspect of the present invention, polyurethane acrylic resins as described in the fourth aspect of the present invention, compositions for photosensitive resins as described in the fifth aspect of the present invention, and photosensitive resins as described in the sixth aspect of the present invention in photocurable coatings, photocurable inks, or 3D printing materials.

[0126] Specifically, a 3D printer, such as a DLP 3D printer, can be used for printing, and the corresponding size can be imported from the 3D model. For example, it can be a 1cm×1cm×1cm cubic lattice, or a strip, dumbbell, or ring shape, or any other form.

[0127] Preparation Example: The preparation method of the aminomethacrylate monomers used in the specific embodiments of the present invention includes the following steps:

[0128] 1) Preparation of TBEEMA: Methyl methacrylate and tert-butylaminoethoxyethanol were added to a reaction vessel in a molar ratio of 3:1. Then, sodium hydroxide (0.6 wt% of the mass of methyl methacrylate), polymerization inhibitor 701 (0.06 wt% of the mass of methyl methacrylate), and antioxidant 1010 (0.8 wt% of the mass of methyl methacrylate) were added. The mixture was then heated to about 105 °C and refluxed for 2 h under stirring. After cooling to room temperature, the precipitate such as sodium hydroxide was removed by centrifugation. The liquid phase was collected and purified to obtain TBEEMA.

[0129] Saturated vapor pressure: The saturated vapor pressure of TBEEMA at 25°C was measured to be 0.308 kPa using a VP2000 vapor pressure meter.

[0130] TBEEMA structural characterization data:

[0131] The mass spectrum of TBEEMA is as follows: Figure 1 As shown, specifically, HRMS-ESI (m / z): Calculated (found) for C12H23NO3 [M+H] + 230;

[0132] The TBEEMA 1H NMR spectrum is as follows: Figure 2 As shown, specifically, 1 ¹H NMR (CDCl₃): δ 6.14–5.58 (m, 2H), 4.31 (m, 2H), 3.71–3.6 (m, 4H), 2.74 (m, 2H), 1.95 (m, H), 1.10 (m, 9H); 2.74 ppm is the chemical shift of the methylene group attached to the amino group in TBEEMA, 3.71 ppm and 3.60 ppm are the chemical shifts of the two methylene groups attached to the ether group, 4.31 ppm is the chemical shift of the methylene group attached to the ester group, 1.95 ppm, 5.58 ppm and 6.14 ppm are the chemical shifts of the methacrylate structure, and 1.10 ppm is the chemical shift of the tert-butyl structure.

[0133] The infrared spectrum of TBEEMA is as follows: Figure 3 As shown, specifically, 3319cm -1 The characteristic absorption peak of NH is at 2961 cm⁻¹. -1 The absorption peak at 1721 cm⁻¹ is the CH stretching vibration peak of the methylene group. -1 The characteristic absorption peak for carbonyl C=O is 1638 cm⁻¹. -1 The absorption peak at 940 cm⁻¹ is the C=C stretching vibration peak. -1 and 1296cm -1 The absorption peak at 1168 cm⁻¹ is due to both out-of-plane bending and in-plane rocking vibrations. -1This is a characteristic absorption peak for COC.

[0134] 2) The preparation of TB(E)2EMA is based on the preparation method of TBEEMA, with the only difference being the use of equimolar amounts of... Replace tert-butylaminoethoxyethanol.

[0135] The preparation method is to react chlorotriethylene glycol and tert-butylamine in acetonitrile under reflux for 8 hours in a molar ratio of 1:1.1, and then obtain the product after conventional post-treatment.

[0136] The TB(E)2EMA product was verified by infrared spectroscopy, and the presence of characteristic absorption peaks of COC and carbonyl C=O confirmed the successful preparation of TB(E)2EMA.

[0137] Saturated vapor pressure: The saturated vapor pressure of TB(E)2EMA at 25°C was measured to be 0.258 kPa using a VP2000 vapor pressure measuring instrument.

[0138] 3) The preparation of TB(E)5EMA is based on the same method as that of TBEEMA, the only difference being the use of equimolar amounts of... Replace tert-butylaminoethoxyethanol.

[0139] The preparation method is as follows: 1) Hexaethylene glycol, p-toluenesulfonyl chloride, and triethylamine in a molar ratio of 1:1:0.5 are reacted in dichloromethane at room temperature for 30 min, and then post-treated to obtain p-toluenesulfonyl hexaethylene glycol. 2) p-Toluenesulfonyl hexaethylene glycol and tert-butylamine in a molar ratio of 1:1 are mixed and reacted at 50 °C for 2 h, and then post-treated to obtain the product.

[0140] The TB(E)5EMA product was verified by infrared spectroscopy, and the presence of characteristic absorption peaks of COC and carbonyl C=O confirmed the successful preparation of TB(E)5EMA.

[0141] Saturated vapor pressure: The saturated vapor pressure of TB(E)5EMA at 25℃ was measured to be 0.095 kPa using a VP2000 vapor pressure measuring instrument.

[0142] 4) The preparation of TB(E)6EMA is based on the preparation method of TBEEMA, with the only difference being the use of equimolar amounts of... Replace tert-butylaminoethoxyethanol.

[0143] The preparation method is as follows: 1) Heptaethylene glycol, p-toluenesulfonyl chloride, and triethylamine in a molar ratio of 1:1:0.5 are reacted in dichloromethane at room temperature for 30 min, and then post-treated to obtain p-toluenesulfonyl heptaethylene glycol. 2) Then, p-toluenesulfonyl heptaethylene glycol and tert-butylamine in a molar ratio of 1:1 are mixed and reacted at 50℃ for 2 h, and then post-treated to obtain the product.

[0144] The TB(E)6EMA product was verified by infrared spectroscopy, and the presence of characteristic absorption peaks of COC and carbonyl C=O confirmed the successful preparation of TB(E)6EMA.

[0145] Saturated vapor pressure: The saturated vapor pressure of TB(E)6EMA at 25°C was measured to be 0.080 kPa using a VP2000 vapor pressure measuring instrument.

[0146] Example 1

[0147] This embodiment provides a composition for photosensitive resins, comprising the following components:

[0148] 100g polyurethane acrylic resin, 20g LMA, 1g photoinitiator TPO, 5.3g DMDC, 0.01g modified silicone defoamer (Tego Airex 978).

[0149] Polyurethane acrylic resin with a molecular weight of 2900 g / mol was obtained by reacting a mixture of terminal isocyanate prepolymer and TBEEMA at 55°C until no NCO absorption peak was detected in the infrared spectrum. The reaction was then stopped. The NCO content in the terminal isocyanate prepolymer was 3.43 wt%, and the molar ratio of NCO groups in TBEEMA to those in the terminal isocyanate prepolymer was 1.05:1.

[0150] The preparation of the terminal isocyanate prepolymer includes reacting polytetrahydrofuran ether diol (number average molecular weight of 2000) and isophorone diisocyanate (IPDI) in a molar ratio of 1:2 at 85°C for 3 h.

[0151] The preparation method of 3D printed products includes: mixing the components of the photosensitive resin composition evenly, printing the sample using a DLP type 3D printer; after printing the sample according to the dimensions imported by the 3D model, curing it at 110℃ for 2 hours to obtain the 3D printed product.

[0152] Example 2

[0153] This embodiment provides a composition for photosensitive resins, comprising the following components:

[0154] 100g of polyurethane acrylic resin, 40g of polyethylene glycol (600) dimethacrylate, 0.3g of photoinitiator 1173, and 2g of 1,4-cyclohexanediamine.

[0155] The polyurethane acrylic resin, with a molecular weight of 3900 g / mol, is specifically produced by reacting a mixture of terminal isocyanate prepolymer and TBEEMA at 55°C until no NCO absorption peak is detected in the infrared spectrum, at which point the reaction is stopped. The NCO content in the terminal isocyanate prepolymer is 2.67 wt%, and the molar ratio of NCO groups in TBEEMA to those in the terminal isocyanate prepolymer is 1.05:1.

[0156] The preparation of the terminal isocyanate prepolymer includes reacting polyethylene adipate diol (number average molecular weight of 3000) and isophorone diisocyanate in a molar ratio of 1:2.1 at 90°C for 2 hours.

[0157] The preparation method of 3D printed articles is the same as in Example 1, except that the photosensitive resin composition in Example 1 is replaced with the photosensitive resin composition of this example.

[0158] Example 3

[0159] This embodiment provides a composition for photosensitive resins, comprising the following components:

[0160] 100g polyurethane acrylic resin, 30g LMA, 3g photoinitiator TPO, 8.5g DMDC, 0.1g modified silicone defoamer (Tego Airex 978).

[0161] The polyurethane acrylic resin, with a molecular weight of 1980 g / mol, was specifically prepared by reacting a mixture of terminal isocyanate prepolymer and TBEEMA at 55°C until no NCO absorption peak was detected in the infrared spectrum, at which point the reaction was stopped. The NCO content in the terminal isocyanate prepolymer was 5.74 wt%, and the molar ratio of NCO groups in TBEEMA to those in the terminal isocyanate prepolymer was 1.05:1.

[0162] The preparation of the terminal isocyanate prepolymer includes reacting polycarbonate diol (number average molecular weight of 1000) and 4'-dicyclohexylmethane diisocyanate (HMDI) in a molar ratio of 1:2.05 at 90°C for 2 h.

[0163] The preparation method of 3D printed articles is the same as in Example 1, except that the photosensitive resin composition in Example 1 is replaced with the photosensitive resin composition of this example.

[0164] Example 4

[0165] This embodiment refers to Embodiment 1, the only difference being that the type of aminomethacrylate monomer used in the preparation of the polyurethane acrylic resin is different, and all other aspects are the same as in Embodiment 1.

[0166] In this embodiment, equimolar amounts of TB(E)2EMA are used to replace TBEEMA in Example 1.

[0167] Example 5

[0168] This embodiment refers to Embodiment 1, the only difference being that the type of aminomethacrylate monomer used in the preparation of the polyurethane acrylic resin is different, and all other aspects are the same as in Embodiment 1.

[0169] In this embodiment, equimolar amounts of TB(E)5EMA are used to replace TBEEMA in Example 1.

[0170] Example 6

[0171] This embodiment refers to Embodiment 1, the only difference being that the type of aminomethacrylate monomer used in the preparation of the polyurethane acrylic resin is different, and all other aspects are the same as in Embodiment 1.

[0172] In this embodiment, equimolar amounts of TB(E)6EMA are used to replace TBEEMA in Example 1.

[0173] Example 7

[0174] This embodiment refers to Embodiment 1, the only difference being that the type of aminomethacrylate monomer used in the preparation of the polyurethane acrylic resin is different, and all other aspects are the same as in Embodiment 1.

[0175] In this embodiment, a mixture of TBEEMA and TB(E)5EMA with a molar ratio of 1:1 is used to replace TBEEMA in Example 1, and the sum of the molar ratios of TBEEMA and TB(E)5EMA in this embodiment is the same as the molar ratio of TBEEMA in Example 1.

[0176] Example 8

[0177] This embodiment is based on Example 1, except that the NCO content in the terminal isocyanate prepolymer is different, resulting in a different molecular weight of the polyurethane acrylic resin prepared. All other aspects are the same as in Example 1.

[0178] In this embodiment, the NCO content in the terminal isocyanate prepolymer is 1.5 wt%, and the resulting polyurethane acrylic resin has a molecular weight of 6060 g / mol.

[0179] Example 9

[0180] This embodiment is based on Example 1, except that the NCO content in the terminal isocyanate prepolymer is different, resulting in a different molecular weight of the polyurethane acrylic resin prepared. All other aspects are the same as in Example 1.

[0181] In this embodiment, the NCO content in the terminal isocyanate prepolymer is 6.5 wt%, and the molecular weight of the polyurethane acrylic resin prepared is 1750 g / mol.

[0182] Example 10

[0183] This embodiment refers to Embodiment 1, the only difference being the amount of LMA used in the photosensitive resin composition. All other aspects are the same as in Embodiment 1.

[0184] In this embodiment, the amount of LMA used is 60g.

[0185] Example 11

[0186] This embodiment refers to Embodiment 1, the only difference being the amount of DMDC in the photosensitive resin composition. All other aspects are the same as in Embodiment 1.

[0187] In this embodiment, the amount of DMDC used is 11g.

[0188] Example 12

[0189] This embodiment refers to Embodiment 1, except that 0.2g of azobisisovalerate is added to the photosensitive resin composition.

[0190] Example 13

[0191] This embodiment refers to Embodiment 2, except that 0.5g of benzoyl peroxide is added to the photosensitive resin composition.

[0192] Example 14

[0193] This embodiment refers to Embodiment 3, except that 1g of dilauryl peroxide is added to the photosensitive resin composition.

[0194] Comparative Example 1

[0195] This comparative example refers to Example 1, the only difference being that the type of aminomethacrylate monomer used in the preparation of the polyurethane acrylic resin is different, and all other aspects are the same as in Example 1.

[0196] In this comparative example, equimolar amounts of tert-butylaminoethyl methacrylate (TBAEMA) were used instead of TBEEMA in Example 1.

[0197] Experimental Example

[0198] 1. For the polyurethane acrylic resins prepared in different embodiments and comparative examples, 5g of 1,4-cyclohexanediamine was added to 100g of resin. After curing at 150℃ for 1.5h, the odor was tested according to QB / T 2725-2005 "Determination of Leather Odor". The odor between two levels was expressed as 1-2, 2-3, 3-4 or 4-5. The test results are shown in Table 1.

[0199] II. The 3D printed products obtained from different embodiments and comparative examples were tested as follows, and the test results are shown in Table 1.

[0200] (1) Odor of 3D printed products: The odor of 3D printed products was tested in accordance with QB / T 2725-2005 "Determination of odor of leather". The odor between two levels is represented as 1-2, 2-3, 3-4 or 4-5. The test results are shown in Table 1.

[0201] (2) Volume shrinkage rate: The density ρ1 of the photosensitive resin after uniform mixing of different implementations and comparative proportions was tested, and then the density ρ2 of the 3D printed product was tested; the volume shrinkage rate was calculated according to (ρ2-ρ1) / ρ1×100%, and the test results are shown in Table 1.

[0202] (3) Glass transition temperature of 3D printed products: The glass transition temperature of 3D printed products was tested by DSC. The test results are shown in Table 1.

[0203] (4) Tensile strength of 3D printed products: The tensile strength of 3D printed products was tested in accordance with GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber". The test results are shown in Table 1.

[0204] (5) Low-temperature folding resistance of 3D printed products: The low-temperature folding resistance of 3D printed products under -20℃ conditions was tested with reference to SATRA TM92.

[0205] Table 1. Test results for different implementations and comparative examples.

[0206]

[0207] The test results above show that the aminomethyl acrylate monomers of the present invention have low saturated vapor pressure and almost no irritating odor at normal operating temperatures. Introducing the aminomethyl acrylate monomers of the present invention into materials such as polyurethane acrylic resins and photosensitive resins can reduce the volume shrinkage rate of photocured products and improve the low-temperature toughness of photocured products.

[0208] The test results of Examples 1 and 4-6 show that as the number of ethoxy groups in the aminomethacrylate monomers increases, the saturated vapor pressure of the monomer decreases, the odor of the corresponding polyurethane acrylic resin and 3D printed products gradually decreases, the glass transition temperature of the 3D printed products gradually decreases, the low-temperature flexural strength gradually improves, but the tensile strength gradually decreases.

[0209] The test results of Examples 1 and 7 show that using two or more aminomethacrylate monomers in combination can also help achieve a good balance between odor, glass transition temperature, low-temperature flexural strength and tensile strength of 3D printed products.

[0210] The test results of Examples 1 and 8-9 show that a suitable NCO content in the terminal isocyanate prepolymer is beneficial to balancing the various properties of 3D printed products. When the NCO content in the terminal isocyanate prepolymer is too low, the viscosity of the mixed system of the photosensitive resin composition is high, and the tensile strength of the 3D printed products is significantly reduced. When the NCO content in the terminal isocyanate prepolymer is too high, the 3D printed products are too hard, resulting in poor low-temperature flexural strength.

[0211] The test results of Examples 1 and 10 show that introducing an appropriate amount of reactive diluent into the photosensitive resin composition can combine the other components to take into account the multiple properties of the 3D printed products. When the amount of reactive diluent is too high, the tensile strength of the 3D printed products decreases and the low-temperature folding resistance deteriorates.

[0212] The test results of Examples 1 and 11 show that introducing an appropriate amount of curing agent into the photosensitive resin composition can combine the other components to take into account the multiple properties of the 3D printed products. When the amount of curing agent is too high, excessive cross-linking leads to a decrease in the low-temperature folding resistance of the 3D printed products.

[0213] By comparing Examples 1, 2, and 3 with Examples 1, 2, and 3 respectively, the photosensitive resin composition incorporates a thermal initiator, which helps to further reduce the odor of 3D printed articles.

[0214] The test results from the examples and Comparative Example 1 show that when the aminomethacrylate monomers of the present invention are not used, the corresponding polyurethane acrylic resin and 3D printed products have obvious odors, the low-temperature folding resistance of the 3D printed products deteriorates significantly, and the volume shrinkage rate of the photosensitive resin composition before and after curing is large.

[0215] In addition, the tactile evaluation of the 3D printed articles prepared in Examples 1-14 and Comparative Example 1 was conducted by direct skin contact. The tactile comfort of the 3D printed articles in Examples 1-14 was higher than that of the 3D printed articles obtained in Comparative Example 1.

[0216] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An aminomethacrylate monomer, characterized in that, It has the following general structural formula as shown in Equation I: ； Where n is selected from integers between 1 and 6.

2. A method for preparing aminomethacrylate monomers, characterized in that, The process includes the following steps: methyl methacrylate undergoes an transesterification reaction with a substance represented by the structure of Formula II. ； Where n is selected from integers between 1 and 6; The aminomethacrylate monomers have the general structural formula shown in Formula I below: 。 3. The preparation method according to claim 2, characterized in that, The transesterification reaction has at least one of the following characteristics: (1) The molar ratio of the methyl methacrylate to the substance represented by the structure of Formula II is (2-4):1; (2) The temperature of the transesterification reaction is 90-120℃; the time of the transesterification reaction is 1-3h.

4. The preparation method according to claim 2, characterized in that, The transesterification reaction has at least one of the following characteristics: (1) The transesterification reaction is carried out under the catalysis of a catalyst; the catalyst includes a solid base; (2) The transesterification reaction is carried out in the presence of a polymerization inhibitor; (3) The transesterification system also includes an antioxidant; (4) The process after the transesterification reaction further includes: solid-liquid separation of the material after the transesterification reaction, collection of the liquid phase, and purification treatment to obtain the product.

5. A composition for polyurethane acrylic resin, characterized in that, It includes at least one of the aminomethacrylate monomers as described in claim 1 and a terminal isocyanate prepolymer; the molar ratio of the aminomethacrylate monomer to the NCO group in the terminal isocyanate prepolymer is (1 to 1.05):

1.

6. The composition for polyurethane acrylic resin according to claim 5, characterized in that, The aminomethacrylate monomers include any one of the following structures: 、 、 、 、 、 。 7. The composition for polyurethane acrylic resin according to claim 5, characterized in that, The raw materials for preparing the terminal isocyanate prepolymer include polymeric polyols and polyisocyanates, and have at least one of the following characteristics: (1) The polymer polyol includes at least one of polyester polyol, polyether polyol, polycaprolactone polyol and polycarbonate polyol; The polymer monomers of the polyester polyol include optional diols with 2 to 10 carbon atoms and optional dicarboxylic acids with 4 to 12 carbon atoms. The polyether polyol includes at least one of polytetrahydrofuran polyol, polyethylene oxide polyol, polypropylene oxide ether polyol, and polyethylene oxide-propylene oxide ether polyol. (2) The number average molecular weight of the polymer polyol is 1000-3000 g / mol; (3) The functionality of the polymer polyol is 2 to 3; (4) The polyisocyanate includes at least one of toluene diisocyanate, terephthalic diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and isophorone diisocyanate; (5) The molar ratio of the polymer polyol and the polyisocyanate is 1:(2 to 2.1). (6) The NCO content in the terminal isocyanate prepolymer is 2wt% to 6wt%.

8. A polyurethane acrylic resin, characterized in that, It is prepared from the polyurethane acrylic resin composition according to any one of claims 5 to 7.

9. The polyurethane acrylic resin according to claim 8, characterized in that, The polyurethane acrylic resin has the following terminal groups: 。 10. The polyurethane acrylic resin according to claim 8, characterized in that, It has at least one of the following characteristics: (1) The molecular weight of the polyurethane acrylic resin is 1500-6200 g / mol; (2) The preparation of the polyurethane acrylic resin includes: reacting a mixture of terminal isocyanate prepolymer and aminomethacrylate monomer at 50-60°C.

11. A composition for photosensitive resins, characterized in that, Includes the polyurethane acrylic resin according to any one of claims 8 to 10.

12. The composition for photosensitive resin according to claim 11, characterized in that, It also includes at least one of reactive diluents, photoinitiators, curing agents, thermal initiators, and defoamers, and has at least one of the following characteristics: (1) The amount of the reactive diluent is 10wt% to 50wt% of the polyurethane acrylic resin; (2) The active diluent includes at least one of isooctyl methacrylate, ethoxyethoxyethyl methacrylate, triethylene glycol dimethacrylate, dodecyl methacrylate and polyethylene glycol dimethacrylate; (3) The amount of the photoinitiator is 0.3wt% to 3wt% of the polyurethane acrylic resin; (4) The photoinitiator includes at least one of photoinitiator TPO, photoinitiator 1173, photoinitiator 184, photoinitiator 819 and photoinitiator TMO; (5) The amount of the curing agent is 4wt% to 10wt% of the polyurethane acrylic resin; (6) The curing agent includes at least one of 3,3-dimethyl-4,4-diaminodicyclohexylmethane, 4,4-diaminodicyclohexylmethane, 1,4-cyclohexanediamine, hexanediamine, octanediamine and decanediamine; (7) The amount of the thermal initiator is 0.1 wt% to 1 wt% of the polyurethane acrylic resin; (8) The thermal initiator includes at least one of azo thermal initiators and peroxide thermal initiators; (9) The amount of the defoamer is 0.01wt% to 0.1wt% of the polyurethane acrylic resin.

13. A photosensitive resin, characterized in that, It is prepared from the photosensitive resin composition according to any one of claims 11 to 12.

14. The photosensitive resin according to claim 13, characterized in that, It has at least one of the following characteristics: (1) The glass transition temperature of the photosensitive resin is -40 to -10℃; (2) The volume shrinkage rate of the photosensitive resin is 2% to 6%.

15. The use of the aminomethacrylate monomer of claim 1, or the composition for polyurethane acrylic resin of any one of claims 5 to 7, or the polyurethane acrylic resin of any one of claims 8 to 10, or the composition for photosensitive resin of any one of claims 11 to 12, or the photosensitive resin of any one of claims 13 to 14, in photocurable coatings, photocurable inks, or 3D printing materials.

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