Light-curable resin composition and application thereof

Abstract

The invention provides a light-curable resin composition and application thereof. The light-curable resin composition comprises the following components: (A) a phthalic acid diacrylic resin modified compound with a structure as shown in a formula I; (B) a further cationically polymerizable compound other than the component (A); (C) a cationic photoinitiator; (D) a radically polymerizable compound; and (E) a radical photoinitiator. In the light-curable resin composition of the present invention, since the specific cationically polymerizable compound is used, a cured product of the light-curable resin composition has excellent heat resistance and maintains high toughness.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a photocurable resin composition and application thereof. Background Art

[0002] In recent years, additive manufacturing has received great attention and interest from the industry and researchers. Since additive manufacturing provides almost unlimited possibilities for rapid prototyping, it has been applied in many research fields, such as mechanical engineering, medicine, materials science and chemistry. With the development and improvement of the process, the number of applications of additive manufacturing has been increasing. However, existing conventional radiation-curable materials suitable for processing by additive manufacturing processes are either tough enough or heat-resistant enough, and often not both. This has greatly affected the application of photosensitive resin materials in the field of 3D printing, so additively manufactured objects are still used as conceptual models rather than functional materials.

[0003] In order to expand the application range of radiation curable compositions in additive manufacturing processes, new materials with high toughness and high heat resistance are desired. Adjusting the crosslink density of the composition is a well-known method in the field of additive manufacturing of radiation curable compositions to change the toughness and heat resistance of the composition. There is a well-known inverse relationship between toughness and heat resistance, that is, as the crosslink density increases, the heat resistance (HDT) of the material increases, but its toughness decreases. Conversely, as the crosslink density decreases, the toughness increases, but the HDT performance suffers.

[0004] Generally, when attempting to increase the heat distortion temperature of a material, a material having a functional group capable of increasing the crosslink density of the cured product or a material having a bulky substituent is selected as the material to be used. When a material having a functional group capable of increasing the crosslink density, such as a multifunctional acrylic or epoxy material, or a material having a bulky substituent, such as an isobornyl group, is used for photocuring, the heat distortion temperature of the cured product increases, but its impact resistance is significantly reduced.

[0005] In order to expand the application range of radiation-curable compositions produced by additive manufacturing processes, new materials with a combination of high toughness and high heat resistance are desired. Achieving this combination of properties will open the door to many new applications, including high-temperature gas / liquid flow prototyping and the manufacture of end-use parts. However, in reality, there is no solution to improve both toughness and heat resistance at the same time to date. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a photocurable resin composition and a preparation method and application thereof. The photocurable resin composition of the present invention can make its cured product have excellent heat resistance and maintain high toughness.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides a photocurable resin composition, comprising the following components:

[0009] (A) a phthalic acid diacrylate resin modified compound having a structure shown in Formula I;

[0010] (B) other cationically polymerizable compounds other than the component (A);

[0011] (C) a cationic photoinitiator;

[0012] (D) a free radical polymerizable compound;

[0013] (E) a free radical photoinitiator;

[0014]

[0015] wherein x and y are each independently selected from integers of 1 to 500 (e.g., 1, 2, 5, 8, 10, 20, 30, 50, 80, 100, 150, 200, 250, 300, 350, 400, 450, or 500); z represents an integer of 1 to 20 (e.g., 1, 2, 3, 5, 8, 10, 12, 15, 18, or 20); the weight average molecular weight of the phthalic acid diacrylate resin modified compound having the structure shown in formula I is 5000 to 100000, and R1 and R2 each independently represent any one of a hydrogen atom, a C1 to C10 straight or branched alkyl group, a C1 to C10 alkoxy group, a C2 to C10 unsaturated hydrocarbon group, a C3 to C10 cycloalkyl group, a C2 to C10 ether group, a halogen atom, or a halogenated hydrocarbon group.

[0016] Since a specific cationically polymerizable compound, i.e., a phthalic acid diacrylate resin modified compound having a structure shown in Formula I, is used in the photocurable resin composition of the present invention, the three-dimensional manufactured product (cured product) produced by the photocurable resin composition has excellent heat resistance and maintains high toughness.

[0017] Preferably, R1 is selected from a hydrogen atom, a C1-C2 straight-chain alkyl group, a C2-C3 ether group, a C1-C2 halogenated hydrocarbon group, and R2 is selected from a hydrogen atom or a methyl group.

[0018] In the formula I described in the present invention, 1:4≤x:y≤4:1, for example, x:y can be 1:4, 1:3, 1:2, 1:1, 2:1, 3:1 or 4:1, preferably 1:1≤x:y≤1.3:1.

[0019] Preferably, the weight average molecular weight of the phthalic acid diacrylate resin modified compound having the structure shown in Formula I is 5000-100000, for example, 5000, 8000, 10000, 12000, 15000, 18000, 20000, 25000, 30000, 40000, 50000, 60000, 70000, 80000, 90000 or 100000.

[0020] Preferably, the x and the y are each independently selected from integers of 20-200, and z is selected from integers of 2-10.

[0021] Preferably, the phthalic acid diacrylate resin modified compound having the structure shown in Formula I is any one of the following compounds:

[0022]

[0023]

[0024] The definitions of x, y, and z are the same as above.

[0025] In the present invention, the preparation method of the phthalic acid diacrylate resin modified compound having the structure shown in Formula I comprises the following steps:

[0026] Step S1: Under an inert gas protective atmosphere, an organic solvent, a diallyl phthalate resin and an oxetane polymer are stirred and mixed uniformly, and the temperature is raised to reflux to obtain a pre-dewatered reaction liquid; the oxetane polymer is a compound shown in structural formula II;

[0027]

[0028] wherein R1 and R2 each independently represent any one of a hydrogen atom, a C1-C10 straight or branched alkyl group, a C1-C10 alkoxy group, a C2-C10 unsaturated hydrocarbon group, a C3-C10 cycloalkyl group, a C2-C10 ether group, a halogen atom and a halogenated hydrocarbon group;

[0029] Step S2: slowly adding a catalyst and raising the temperature to reflux to react, thereby obtaining a diallyl phthalate resin modified compound.

[0030] Preferably, the weight average molecular weight of the compound represented by structural formula II is 250-1100, for example, 250, 300, 500, 800, 1000 or 1100.

[0031] Preferably, in step S1, the mass ratio of the diallyl phthalate resin to the oxetane polymer is 10:1 to 1:10; for example, 10:1, 9:1, 8:1, 5:1, 3:1, 2:1, 1:1, 1:3, 1:5, 1:8, 1:10, preferably 3:1 to 1:10.

[0032] Preferably, the weight average molecular weight of the diallyl phthalate resin in step S1 is 5000-80000, for example, 5000, 6000, 7000, 10000, 30000, 50000, or 80000, more preferably 10000-60000, further preferably 30000-50000.

[0033] Preferably, in step S1, the inert gas includes any one of nitrogen, argon, helium, krypton and neon, or a combination of at least two of them.

[0034] Preferably, the organic solvent in step S1 includes any one or a combination of at least two of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane and chloroform.

[0035] Preferably, the viscosity of the oxetane polymer at 25° C. is 5 to 500 cps, for example, 5 cps, 8 cps, 10 cps, 13 cps, 15 cps, 20 cps, 50 cps, 80 cps, 100 cps, 200 cps, 300 cps, 400 cps or 500 cps, more preferably 10 to 300 cps, and further preferably 20 to 200 cps.

[0036] Preferably, in step S2, the catalyst includes any one of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate and tribenzyl aluminate, or a combination of at least two thereof.

[0037] Preferably, the reflux temperature of steps S1 and S2 is 25-250°C, for example, 25°C, 30°C, 50°C, 80°C, 100°C, 130°C, 150°C, 180°C, 200°C or 250°C, preferably 60-180°C, more preferably 80-160°C.

[0038] Preferably, after the reaction in step S2 is completed, a separation and purification step is also included.

[0039] Preferably, the separation and purification specifically comprises the following steps: step S31: subjecting the crude solution of diallyl phthalate resin modified compound to reduced pressure distillation to obtain a diallyl phthalate resin modified compound concentrate; step S32: subjecting the diallyl phthalate resin modified compound concentrate to crystallization and washing with a poor solvent, filtering, and drying to obtain a compound.

[0040] Preferably, the pressure of the reduced pressure distillation in step S31 is 10-500 mbar (for example, 10 mbar, 30 mbar, 50 mbar, 100 mbar, 200 mbar, 300 mbar, 400 mbar or 500 mbar), and the temperature is 25-120°C (for example, 25°C, 30°C, 50°C, 80°C, 100°C, 110°C or 120°C); more preferably, the solvent evaporated by the reduced pressure distillation is recovered and reused.

[0041] Preferably, the poor solvent in step S32 includes any one of methanol, ethanol, ethyl ether, ethylene glycol monomethyl ether, n-hexane, n-octane and petroleum ether, or a combination of at least two thereof.

[0042] Preferably, based on the total weight of the photocurable resin composition as 100%, the content of the component (A) in the photocurable resin composition is 3 to 10% by weight, for example, 3%, 5%, 8%, 9% or 10% by weight, more preferably 3 to 7% by weight. If the content of the component (A) is too low, the temperature resistance of the cured product is not fully reflected. If the content of the component (A) is too high, the viscosity of the resin composition increases, affecting printing.

[0043] Preferably, the other cationically polymerizable compounds other than the component (A) include at least one of a cyclic ether component, a cyclic lactone component, a cyclic acetal component, a cyclic thioether component, a spirocyclic orthoester, an epoxy-functional component or an oxetane-functional component, preferably at least one of an epoxy-functional component or an oxetane-functional component, and further preferably a combination of an epoxy-functional component and an oxetane-functional component.

[0044] The epoxy functional component used in the present invention includes a type of glycidyl group or epoxycyclohexyl group in the molecule. The number of oxirane structures in each epoxy functional component molecule is at least 1, preferably 2 to 15, and more preferably 2 to 8. In the present invention, the epoxy functional component is used in combination with an oxetane compound to increase the photocuring rate, especially to improve the curability.

[0045] As the epoxy functional component of the present invention, it includes compounds containing epoxy cyclohexyl groups and compounds containing glycidyl groups. Compounds containing epoxy cyclohexyl groups show excellent cationic polymerizability. Compounds containing glycidyl groups provide flexibility to polymers and can increase the mobility of the polymerization system, thereby further improving curability.

[0046] Examples of suitable epoxycyclohexyl-containing compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis( 3,4-epoxycyclohexyl) substituted methane, di(3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene-bis(3,4-epoxycyclohexane) carboxylate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, etc. The epoxycyclohexyl group-containing compound suitable as component (B) includes one or a combination of at least two of the above compounds.

[0047] Among these compounds, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, trimethylcaprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and β-methyl-δ-valerolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate are preferred. 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate and bis(3,4-epoxycyclohexylmethyl) adipate are more preferred.

[0048] As suitable compounds available on the market, there are listed below: UVR-6100, UVR-6105, UVR-6110, UVR-6128, UVR-6200, UVR-6216 (produced by Union Carbide Corporation), Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolead GT-300, Epolead GT-301, Epolead GT-302, Epolead GT-400, Epolead GT-401, Epolead GT-403 (produced by Daicel Chemical Industries, Ltd.), KRM-2100, KRM-2110, KRM-2199 (produced by Asahi Denka Kogyo Co., Ltd.), etc. These compounds can be used alone or in combination of two or more.

[0049] Preferably, the glycidyl group-containing compound suitable as component (B) includes diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of brominated bisphenol A, diglycidyl ether of brominated bisphenol F, diglycidyl ether of brominated bisphenol S, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of hydrogenated bisphenol S, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerol, Trimethylolpropane triglycidyl ether, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, etc.; polyglycidyl ether of polyether polyol, which is obtained by adding one or more olefin oxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol; diglycidyl ester of aliphatic long-chain dibasic acid; monodiglycidyl ether of aliphatic higher alcohol; monodiglycidyl ether of polyether alcohol obtained by adding phenol, cresol, butylphenol, or olefin oxides to them; and glycidyl ester of higher fatty acid, etc. Glycidyl group-containing compounds suitable as component (B) include one or a combination of at least two of the above compounds.

[0050] Among these compounds, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerol, trimethylolpropane triglycidyl ether, diglycidyl ether of neopentyl glycol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol are preferred.

[0051] As suitable compounds containing a glycidyl group that can be purchased from the market, they are listed as follows: UVR-6216 (produced by Union Carbide Corporation), Glycidole, AOEX24, CyclomerA200 (produced by Daicel Chemical Industries, Ltd.), Epicoat828, Epicoat812, Epicoat1031, Epicoat872, EpicoatCT508 (produced by Yuka-Shell KK), KRM-2400, KRM-2410, KRM-2408, KRM-2490, KRM-2720, KRM-2750 (produced by Asahi Denka Kogyo Co., Ltd.), etc.; these compounds can be used alone or in combination of two or more.

[0052] Oxetane compounds suitable as component (B) include 3-ethyl-3-hydroxymethyloxetane, 3-(methyl)allyloxymethyl-3-ethyloxetane, (3-ethyl-3-oxetanylmethoxy)toluene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, [1-(3-ethyl-3-oxetanylmethoxy)methyl]benzene, phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanyl methyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanyl methyl) ether, isobornyl (3-ethyl-3-oxetanyl methyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanyl methyl) ether, ethyl diglycol (3-ethyl-3-oxetanyl methyl) ether, dicyclopentadienyl (3-ethyl-3-oxetanyl methyl) ether, Dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofuranyl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl ( 3-ethyl-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether.3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methylene)propylenediylbis(oxymethylene)bis(3-ethyloxetanyl), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis[(3-ethyl-3-oxetanylmethyl)methyl]ether, dicyclopentenylbis(3-ethyl-3 -oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyl dimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, Pentaerythritol tetra(3-ethyl-3-oxetanyl methyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanyl methyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanyl methyl) ether, dipentaerythritol penta(3-ethyl-3-oxetanyl methyl) ether, dipentaerythritol tetra(3-ethyl-3-oxetanyl methyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanyl methyl) ether, caprolactone-modified dipentaerythritol penta(3-ethyl-3-oxetanyl methyl) ether, ditrimethylolpropane tetra( 3-ethyl-3-oxetanyl methyl) ether, ethylene oxide-modified bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, propylene oxide-modified bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, ethylene oxide-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, propylene oxide-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanyl methyl) ether, ethylene oxide-modified bisphenol F bis(3-ethyl-3-oxetanyl methyl) ether, and the like. These compounds may be used alone or in combination of two or more.

[0053] Among these compounds, compounds having 1 to 10, preferably 1 to 4, more preferably two oxetane rings are suitable as component (B) of the resin composition of the present invention. Examples of the most suitable oxetane compounds are 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-oxetanylmethoxy)toluene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)]ethane, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl)ether, 3-ethyl-3-oxetanylmethoxybenzene, and these compounds can be used alone or in combination of two or more.

[0054] As applicable oxetane compounds that can be purchased from the market, they are listed as follows: TR-TCM101, TR-TCM102, TR-TCM104, TR-TCM109, TR-TCM121, TR-TCM201, TR-TCM207, TR-TCM218, TR-TCM245 (from Changzhou Qiangli Electronic New Materials Co., Ltd.), and the like.

[0055] The component (B) in the resin composition of the present invention is preferably a combination of an epoxy compound and an oxetane compound, which can increase the photocuring rate, and especially improve the curability.

[0056] Preferably, based on the total weight of the photocurable resin composition as 100%, the content of component (B) is 10 to 90 weight%, for example, 10 weight%, 20 weight%, 30 weight%, 40 weight%, 50 weight%, 60 weight%, 70 weight%, 80 weight% or 90 weight%, more preferably 50 to 70 weight%.

[0057] Preferably, the cationic photoinitiator is selected from one or a combination of at least two of an iodonium salt photoinitiator, a sulfonium salt photoinitiator, and an arylferrocenium salt photoinitiator.

[0058] Based on comprehensive considerations such as cost, effects of combined use such as photoinitiator efficiency, curing speed, etc., component (C) is preferably an iodonium salt photoinitiator and / or a sulfonium salt photoinitiator, and particularly preferably at least one of the compounds having the structure shown in the following formula (I) or (II):

[0059]

[0060] wherein R3 and R4 each independently represent hydrogen, a C1-C20 straight or branched alkyl group, a C4-C20 cycloalkylalkyl group or an alkylcycloalkyl group, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;

[0061] R5 and R6 each independently represent hydrogen, C1-C20 straight or branched alkyl, C4-C20 cycloalkylalkyl or alkylcycloalkyl, C6-C20 substituted or unsubstituted aryl, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;

[0062] R7 represents a C6-C20 substituted or unsubstituted aryl group, a C6-C20 substituted or unsubstituted alkylaryl group, a C1-C20 straight-chain or branched alkyl group, a C4-C20 cycloalkylalkyl group or an alkylcycloalkyl group, or a substituted or unsubstituted phenylthiophenyl group, and the non-cyclic -CH2- in these groups may be optionally substituted by a carbonyl group, -O-, -S- or a 1,4-phenylene group;

[0063] R8 and R9 each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an alkyl-substituted or unsubstituted amino group, a cyano group, a nitro group, or a halogen atom;

[0064] m1 and m2 represent the number of R8 and R9 respectively, and are independently integers of 1-4, such as 0, 1, 2, 3 or 4.

[0065] X each independently represents M-, ClO4-, CN-, HSO4-, NO3-, CF3COO-, (BM4)-, (SbM6)-, (AsM6)-, (PM6)-, Al[OC(CF3)3]4-, sulfonate ion, B(C6M5)4- or [(Rf) b PF6-b]-, wherein M is a halogen (such as F, Cl, Br, I), Rf each independently represents an alkyl group in which ≥80% of the hydrogen atoms are substituted by fluorine atoms, and b represents an integer of 1-5.

[0066] As a preferred structure, among the compounds represented by formula (I) and (II):

[0067] R3 and R4 each independently represent hydrogen, C1-C12 straight chain or branched alkyl, C4-C10 cycloalkylalkyl or alkylcycloalkyl, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-;

[0068] R5 and R6 each independently represent hydrogen, C1-C10 straight or branched alkyl, C4-C10 cycloalkylalkyl or alkylcycloalkyl, C6-C12 substituted or unsubstituted aryl, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;

[0069] R7 represents a C6-C10 substituted or unsubstituted aryl group, a C6-C10 substituted or unsubstituted alkylaryl group, or a substituted or unsubstituted phenylthiophenyl group, and the non-cyclic -CH2- in these groups may be optionally substituted by a carbonyl group, -O-, -S- or 1,4-phenylene group;

[0070] R8 and R9 represent C1-C10 straight-chain or branched alkyl, C1-C10 straight-chain or branched alkoxy, C1-C10 alkylcarbonyl and halogen.

[0071] More preferably, the cationic part of the iodonium salt photoinitiator and / or the sulfonium salt photoinitiator can be listed as follows:

[0072]

[0073]

[0074]

[0075] More preferably, the anion part of the iodonium salt photoinitiator or sulfonium salt photoinitiator can be listed as: Cl-, Br-, PF6-, SbF6-, AsF6-, BF4-, C4F9SO3-, B(C6H5)4-, C8F 17 SO3-, CF3SO3-, Al[OC(CF3)3]4-, (CF3CF2)2PF4-, (CF3CF2)3PF3-, [(CF3)2CF2]2PF4-, [(CF3)2CF2]3PF3-, [(CF3)2CFCF2]2PF4-, (CF3)2CFCF2]3PF3-.

[0076] Commercially available cationic photoinitiators with similar structures can also be used for component (C) of the present invention, such as but not limited to PAG20001, PAG20002, PAG30201, PAG30101, etc. produced by Changzhou Qiangli Electronic New Materials Co., Ltd., and Irgacure250 produced by BASF, Germany.

[0077] In addition, in order to improve light efficiency or match a light source of a specific wavelength, a sensitizer may be added. Suitable sensitizers may be anthracene, coumarin or pyrazoline sensitizers. Specifically, preferred sensitizers may be those anthracene sensitizers described in Chinese invention patent applications with application numbers 201510355839.1, 201510355364.6, and 201510353754.X, which are hereby incorporated in their entirety for supplement and reference.

[0078] Preferably, based on the total weight of the photocurable resin composition as 100%, the content of component (C) is 0.1 to 10 wt%, for example, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt% or 10 wt%.

[0079] In the present invention, the photocurable resin composition further includes a radical polymerizable compound.

[0080] The present invention may include one or at least two free radically polymerizable compounds, such as one or at least two free radically polymerizable components containing one or at least two ethylenically unsaturated groups, such as (meth)acrylate (ie, acrylate and / or methacrylate) functional components.

[0081] Preferably, the free radical polymerizable compound includes a monofunctional ethylenically unsaturated component and / or a multifunctional ethylenically unsaturated component. The multifunctional ethylenically unsaturated component refers to a difunctional or higher ethylenically unsaturated component.

[0082] Preferably, examples of the monofunctional ethylenically unsaturated component include acrylamide, N,N-dimethylacrylamide, (meth)acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth)acrylate, isobutoxymethyl (meth)acrylamide, isobornyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, (meth)acrylamide, any one or a combination of at least two of tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, N-vinyl pyrrolidone, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, bornyl (meth)acrylate or methyl triethylene glycol (meth)acrylate.

[0083] Preferably, examples of the multifunctional ethylenically unsaturated component include ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecane diyl dimethylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicapped (meth)acrylic acid addition product of bisphenol A diglycidyl ether, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, Any one of polyethylene glycol di(meth)acrylate, a pentaerythritol derivative with a (meth)acrylate functional group (for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol tetra(meth)acrylate), di(trimethylolpropane) tetra(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated modified hydrogenated bisphenol A di(meth)acrylate or ethoxylated bisphenol F di(meth)acrylate, or a combination of at least two thereof.

[0084] In one embodiment, the free radical polymerizable compound includes one or at least two components containing at least 3 (meth)acrylate groups (eg, 3 to 6 (meth)acrylate groups or 5 to 6 (meth)acrylate groups).

[0085] In the present invention, the content of component (D) is 5 to 60% by weight, for example 5%, 8%, 10%, 15%, 20%, 30%, 40% or 50% by weight. The weight ratio of component D in the composition of the present invention is generally not more than 60%, more preferably less than 40%, or less than 30%.

[0086] The composition of the present invention can use one or at least two free radical photoinitiators. Examples of free radical photoinitiators include benzophenones (e.g., benzophenone, alkyl-substituted benzophenone or alkoxy-substituted benzophenone); benzoins, such as benzoin, benzoin ethers (benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin phenyl ether) and benzoin acetate; acetophenones, such as acetophenone, 2,2-dimethoxyacetophenone, 4-(phenylthio)acetophenone and 1,1-dichloroacetophenone; benzil, benzil ketal (e.g., benzil dimethyl ketal and benzil diethyl ketal); anthraquinones, such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; triphenyl Phosphines; benzoylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide; thioxanthones and xanthones, acridine derivatives, phenazine derivatives, quinoline derivatives or 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-aminophenones or 1-hydroxyphenones, for example 1-hydroxycyclohexylphenone, phenyl(1-hydroxyisopropyl)ketone and 4-isopropylphenyl(1-hydroxyisopropyl)ketone, or triazine compounds, for example 4′″-methylthiophenyl-1-bis(trichloromethyl)-3,5-S-triazine, S-triazine-2-(stilbene)-4,6-bis(dichloromethyl) and p-methoxystyryltriazine.

[0087] In the present invention, other suitable free radical photoinitiators include ionic dye-counter ion compounds, which can absorb actinic rays and generate free radicals, which can initiate the polymerization reaction of acrylates. For example, see those free radical photoinitiators described in the published U.S. Patents US4751102, US4772530 and US4772541, which are incorporated herein in their entirety for supplementation and reference.

[0088] In the present invention, based on the total weight of the photocurable resin composition as 100%, the content of component (E) is 0.01-15% by weight, for example, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 3% by weight, 5% by weight, 8% by weight, 10% by weight, 12% by weight or 15% by weight, preferably 0.1 to 15% by weight, and further preferably 1 to 10% by weight.

[0089] Preferably, the photocurable resin composition further comprises other conventional additives.

[0090] Preferably, the other conventional additives include any one or a combination of at least two of stabilizers, tougheners, fillers, dyes, pigments, antioxidants, wetting agents, defoamers, chain transfer agents, thickeners, leveling agents, defoamers, UV absorbers or surfactants.

[0091] Stabilizers are generally added to the resin composition, and stabilizers that can prevent viscosity increase during use include butylated hydroxytoluene ("BHT"), 2,6-di-tert-butyl-4-hydroxytoluene, hindered amines (e.g., benzyl dimethylamine ("BDMA")), N,N-dimethylbenzylamine, and boron complexes. If used, the stabilizer can be used in an amount of about 0.001% to about 5%, based on 100% by weight of the total weight of the photocurable resin composition.

[0092] Tougheners are usually added to the resin composition, and such tougheners can be reactive and / or non-reactive core-shell types. For example, reactive particles having a cross-linked elastomeric core and a shell containing reactive groups are included. The core of the reactive particles can be composed of polysiloxane, polybutadiene, polybutadiene-co-styrene, amine-terminated polybutadiene, methacrylated polybutadiene, alkyl acrylate, polyorganosiloxane, rubber, poly(ethylene glycol)-modified urethane acrylate, polyurethane acrylate polycarbonate, PTFE or other elastomeric materials. In one embodiment, the cross-linked core is composed of polysiloxane. In another embodiment, the polysiloxane core is a cross-linked polyorganosiloxane, which can include dialkylsiloxane repeating units, wherein the alkyl group is a C1-6 alkyl group. In another embodiment, the polysiloxane core includes dimethylsiloxane repeating units. The shell containing reactive groups can be composed of poly(styrene-co-acrylonitrile), poly(acrylonitrile), poly(carboxyl-functionalized PMMA-co-styrene), polystyrene-co-butyl acrylate, polystyrene, poly(methyl methacrylate-co-maleic anhydride), poly(alkyl methacrylates), poly(styrene-co-acrylonitrile), polystyrene, poly(methyl methacrylate-co-styrene), poly(styrene-co-acrylonitrile), modified vinyl esters, epoxides, PMMA, polyglycidyl methacrylate-co-acrylonitrile, poly(cyclohexanedimethylene terephthalate), thermoplastic resins such as polycarbonate, poly(methyl methacrylate-co-glycidyl methacrylate), poly(methyl methacrylate-co-acrylonitrile-co-divinylbenzene). The reactive groups of the shell can be epoxy groups, oxetane groups, ethylenically unsaturated groups, and / or hydroxyl groups. In one embodiment, the reactive groups may be oxirane, glycidyl, vinyl ester, vinyl ether, acrylate groups, and mixtures thereof. The average particle size of the reactive particles is preferably about 0.01 to 50 μm, more preferably about 0.1 to 5 μm, and even more preferably about 0.1 to about 3 μm. Examples of commercially available reactive particles include Albidur EP 2240, silicone-epoxide particles in bisphenol A epoxy resin; Albidur VE 3320, silicone-vinyl ester particles in bisphenol vinyl ester; and Albidur EP 5340, silicone-epoxide particles in alicyclic epoxy resin (all available from Hanse Chemie). In one embodiment, the reactive particles are added to the photocurable composition in the form of a mixture of reactive particles and a reactive liquid medium containing, for example, epoxide or ethylenically unsaturated groups.For example, for Albidur EP 2240, the reactive organosiloxane particles are dispersed in bisphenol A glycidyl ether, for Albidur VE 3320 in bisphenol A vinyl ester and for Albidur EP 5340 in cycloaliphatic epoxide. The amount of reactive particles added to the photocurable composition can vary depending on the cationically curable component and the free radically active component. When present, the photocurable composition can contain at least about 0.5 wt%, more preferably at least about 1 wt%, and even more preferably at least about 1.5 wt%, based on the total weight of the photocurable resin composition as 100%. In another embodiment, the reactive particles are present in an amount of up to about 40 wt%, more preferably up to about 15 wt%, and even more preferably up to about 10 wt%, based on the total weight of the photocurable resin composition as 100%. In another embodiment, the reactive particles are present in the range of about 0.01 to 40 wt %, preferably about 0.5 to 15 wt %, and even more preferably about 1 to 5 wt %, based on 100 wt % of the total weight of the photocurable resin composition.

[0093] Other toughening agents that can be added to the resin composition include one or more hydroxyl-containing compounds. The hydroxyl-containing compound has a functionality of at least 1 and more preferably at least 2, and is free of any group that inhibits the curing reaction. The hydroxyl-containing compound can be an aliphatic or aromatic hydroxyl-containing compound. Examples include polyether polyols, polyester polyols, hydroxyl and hydroxyl / epoxy functionalized polybutadiene, 1,4-cyclohexanedimethanol, polycaprolactone diols and triols, ethylene / butylene polyols, and monohydroxyl functional monomers. In one embodiment, the hydroxyl-containing compound is polytetramethylene ether glycol ("polyTHF"). The molecular weight of the polyTHF is preferably 250 to 2500, and can be terminated with hydroxyl, epoxy, or ethylenically unsaturated groups. Commercially available polyTHF includes Polymeg 1000, which is a linear diol with a nominal molecular weight of 1000. In another embodiment, the hydroxyl functional compound is a caprolactone-based oligo- or polyester, for example, trimethylolpropane-triester with caprolactone, such as Tone 301. In another embodiment, the hydroxyl functional compound is a polyester, such as k-flex 188. When present, the total amount of the hydroxyl functional compound that can be added to the photocurable composition can generally be about 0.01 to 40 wt%, and preferably about 0.5 to 20 wt%, based on the total weight of the photocurable resin composition as 100%.

[0094] Other possible additives include organic and inorganic fillers, dyes, pigments, antioxidants, wetting agents, defoamers, chain transfer agents, thickeners, leveling agents, defoamers, UV absorbers, surfactants, nanofillers with an average particle size of 3 to 50 nm, etc. Such additives are generally known to those skilled in the art and can be used according to the needs of a specific application.

[0095] Fillers may also be added, including inorganic or organic, powdered, flaky or fibrous materials. Examples of inorganic fillers include mica, glass or silica, calcium carbonate, barium sulfate, talc, glass or silica foam, zirconium silicate, iron oxide, glass fiber, asbestos, diatomaceous earth, dolomite, powdered metal, titanium oxide, pulp powder, kaolin, modified kaolin, hydrated kaolin metal fillers, ceramics and composite materials. Examples of organic fillers include polymer compounds, thermoplastics, core-shell, aromatic polyamides, Kevlar, nylon, cross-linked polystyrene, cross-linked poly(methyl methacrylate), polystyrene or polypropylene, cross-linked polyethylene powder, cross-linked phenolic resin powder, cross-linked urea resin powder, cross-linked melamine resin powder, cross-linked polyester resin powder and cross-linked epoxy resin powder. Optionally, both inorganic and organic fillers may be surface treated with various compound-coupling agents. Examples include methacrylpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidylpropyltrimethoxysilane, and methyltriethoxysilane. Mixtures of inorganic and organic fillers may also be used. Other examples of preferred fillers are microcrystalline silica, crystalline silica, amorphous silica, alkaline aluminum silicate, feldspar, aluminum oxide, aluminum hydroxide, glass powder, aluminum trihydrate, surface treated aluminum trihydrate, and aluminum silicate. Each of the preferred fillers is commercially available. The most preferred fillers are inorganic fillers such as silica, Imsil, Novasite, amorphous silica, feldspar, and aluminum trihydrate. These fillers are preferably transparent to UV light, have a low tendency to refract or reflect incident light, and provide good dimensional stability and heat resistance. Nanofillers such as exfoliated clays (nanoclays), nanosilica, aluminum borate whiskers, nanobarium sulfate, silica nanoparticles dispersed in a UV-curable monomer, aluminum oxide nanoparticles dispersed in a UV-curable monomer may also be used.

[0096] The fillers and nanofillers used in the resin composition for stereolithography of the present invention must also meet the requirement that they do not hinder cationic or free radical polymerization, and the filled composition has a relatively low viscosity suitable for stereolithography. The fillers and nanofillers can be used alone or as a mixture of two or more fillers, depending on the desired properties. The fillers and nanofillers used in the present invention can be neutral, acidic or alkaline, with weak alkaline being preferred. It can vary between 50nm and 50μm. The nanofiller particle size can vary between 3 and 500nm. Dispersants can be used to ensure good dispersion of these nanofillers.

[0097] If present, the filler content in the photocurable composition can generally be about 0.5 wt % to about 30 wt %, based on the total weight of the photocurable resin composition as 100%. The curable composition of the present invention can be prepared in a known manner, for example, by premixing the individual components and then mixing the premixes, or by mixing all the components together using conventional equipment such as a stirring tank. In one embodiment, the mixing is carried out in the absence of light and, if desired, at a slightly elevated temperature in the range of about 30° C. to about 60° C. In addition, it is desirable that the photocurable composition has a viscosity at 25° C. in the range of 50 to 1000 cps, more preferably 70 to 700 cps.

[0098] The novel resin composition can be polymerized by irradiation with light, for example by means of electron beams, X-rays, UV or VIS light, preferably irradiated in the wavelength range of 280 to 650 nm. Particularly suitable are HeCd, argon ion or nitrogen laser beams, as well as metal vapor and NdYAG lasers. The present invention can employ various types of existing or developing lasers, such as solid-state, argon ion lasers, etc., as well as radiation that is not based on lasers. Those skilled in the art will appreciate that for each selected light source, an appropriate photoinitiator and a suitable sensitizer must be selected.

[0099] In another aspect, the present invention provides a three-dimensional article, wherein the three-dimensional article is prepared from the photocurable resin composition as described above.

[0100] The three-dimensional article is prepared in continuous cross-sectional layers according to the article model, and the preparation method is: by forming a first layer of the photocurable composition; exposing the first layer to actinic radiation with a pattern corresponding to each cross-sectional layer of the model, sufficient to harden the first layer in the imaging area; forming a second layer of the photocurable composition on the hardened first layer; exposing the second layer to actinic radiation with a pattern corresponding to each cross-sectional layer of the model, sufficient to harden the second layer in the imaging area; and repeating the above two steps to form the desired continuous layers, thereby forming a three-dimensional article, which can be used in various applications, such as aerospace industry and investment casting, or for medical applications.

[0101] In another aspect, the present invention provides use of the photocurable resin composition as described above in stereolithography or three-dimensional inkjet printing.

[0102] Although the photocurable composition of the present invention is preferably used in a stereolithography process, it may also be used in three-dimensional inkjet printing or other rapid prototyping techniques to produce three-dimensional articles.

[0103] In inkjet printing, continuous droplets of the photocurable composition (e.g., using an inkjet print head such as a piezoelectric inkjet print head) are applied to a substrate at a target location and radiated by exposing the liquid to electromagnetic radiation, thereby causing the composition to solidify and form a three-dimensional product of a desired shape. The droplets are deposited according to the desired shape stored in a computer folder (e.g., a CAD folder). The substrate may include paper, fabric, tile, printing plate, wallpaper, plastic, or paste. The photocurable composition may be radiated pixel by pixel, row by row, or layer by layer after several layers have been formed, and / or after all layers have been formed. The electromagnetic radiation employed may be UV light, microwave radiation, visible light, a laser beam, or other similar sources.

[0104] Alternatively, the photocurable composition of the present invention can be deposited on a powder. The powder can be spread on a substrate as a thin layer and the photocurable composition can be spray-deposited on the powder at the desired position in the desired pattern. The pattern can then be cured by exposing the photocurable composition to UV light. Another layer of powder is then placed on top of the first layer, and the process is repeated to form the three-dimensional product. After forming the three-dimensional product, any uncured powder can be removed. After removing the uncured powder, the last heat and / or radiation curing can be provided to obtain the three-dimensional product. Thus the photocurable composition is completely accumulated with the powder.

[0105] In another aspect, the present invention provides use of the photocurable resin composition as described above or the three-dimensional product as described above in aerospace industry materials, medical supplies, coatings or light emitting diode materials.

[0106] The resin compositions of the invention may be used in areas including as adhesives, as coatings, for example, photoimageable coatings such as photoresists, or coatings for optical fibers, as sealants for light emitting diodes, or in paints, inks or varnishes or any other application, process or method in which a shelf-stable photocurable composition having stable mechanical properties upon curing is desired.

[0107] Compared with the prior art, the present invention has the following beneficial effects:

[0108] The photocurable resin composition of the present invention can provide a cured product thereof with excellent heat resistance and maintain high toughness. DETAILED DESCRIPTION

[0109] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0110] Example

[0111] Representative embodiments of the present invention will be described as examples, and the present invention will not be limited thereto. Samples were prepared according to the proportions of the components in Table 1. In the following examples, all parts are by weight. The formulations described in the examples were prepared by mixing the components, stirring with a stirrer at 20-80° C. (depending on viscosity) in a yellow light room until a uniform composition was obtained, and most formulations were stirred at room temperature of 25-30° C. to form a uniform composition.

[0112] Table 1: Examples 1 to 9 and Comparative Examples 1 to 3

[0113]

[0114]

[0115] Resin 1: Mw≈59000;

[0116] Resin 2: Mw≈61000;

[0117] Resin 3: Mw≈49000;

[0118] Resin 4: Mw≈57000

[0119] Resin 5: Mw≈64000

[0120] Resin 6: Mw≈71000;

[0121] Resin 7: Mw≈35000 (purchased from Japan Daisou Chemical Industry Co., Ltd., DAP resin).

[0122] The preparation method of resins 1-6 is the same as the preparation method of the resins in the examples in patent CN202211304277.4.

[0123] TTA21: 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (Jiangsu Taitel New Materials)

[0124] EPX-152: Nano-core-shell toughened epoxy (LOHO)

[0125] TCM101: 3-Ethyl-3-oxetanol (Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0126] SR399: Polydipentaerythritol pentaacrylate (Sartomer)

[0127] DPHA: Dipentaerythritol pentaacrylate (Sartomer)

[0128] PETA: Pentaerythritol triacrylate (Changzhou Taihan Chemical)

[0129] TMCHA: 3,3,5-Trimethylolcyclohexyl acrylate (Changxing Chemical)

[0130] PAG201: Triaryl sulfonium hexafluoroantimonate salt (Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0131] 184: 1-Hydroxy-cyclohexyl-phenyl ketone (Changzhou Qiangli Electronic New Materials Co., Ltd.)

[0132] BYK A501: Defoamer (BYK)

[0133] The photosensitive resin compositions of the embodiments and comparative examples were subjected to comparative tests on formulation viscosity, critical exposure energy Ec, curing depth Dp, flexural strength, flexural modulus, tensile strength, elongation at break, heat deformation temperature and notched impact strength.

[0134] Among them, the test methods of various performance indicators are as follows:

[0135] 1. Working filling scanning rate: Use an SLA 3D printer (equipment model: Lite 1000 produced by Liantai) to perform scanning and curing at a fixed power of 320mW. The maximum filling scanning rate that can solidify the liquid material and take it out for cleaning is the working filling scanning rate of the material. This indicator directly reflects the curing rate of the photosensitive resin composition. The higher the working filling scanning rate of the material, the higher the molding efficiency of the material;

[0136] 2. The tensile strength and elongation at break are tested according to ASTM D638;

[0137] 3. The flexural modulus and flexural strength are tested according to ASTM D638;

[0138] 4. Heat deformation temperature HDT test is carried out according to standard ASTM D648;

[0139] 5. The notched impact strength test is carried out according to the standard ASTM D256;

[0140] Before testing the mechanical properties and heat deformation temperature of the printed parts, the printed parts need to be post-cured. The post-curing conditions are: post-curing in a UV post-curing box (30W) for 20 minutes, and then testing after normal placement for 24 hours.

[0141] The performance test results are shown in Table 2 and Table 3.

[0142] Table 2

[0143]

[0144]

[0145] Table 3

[0146]

[0147] From Table 2 and Table 3, it can be seen that the viscosity of the photocurable resin composition of the present invention can reach 480-693 cps, and the critical exposure energy Ec is 8-10.63 mJ / cm 2 , the curing depth Dp is 0.11-0.13mm, the bending strength of the cured product is 75-85.5MPa, the bending modulus is 2113-2374MPa, the tensile strength is 52-68MPa, the elongation at break is 5.1-8.3%, the heat deformation temperature is 70.3-77.5℃, and the notched impact strength is 19.7-27.6J / m.

[0148] The polymerizable polymer resin provided in each embodiment of the present invention has a suitable viscosity of the photosensitive resin within the addition range of 3%-10%, has a good improvement in the heat resistance of the three-dimensional manufacturing material, and has good toughness. However, when the addition amount is greater than 10%, the formula viscosity is high, and printing failure is prone to occur. Unmodified resin 7, due to the low reactivity of the allyl functional group, cannot participate in radiation curing well, and the excellent performance of the polymer material is not reflected in the material performance.

[0149] The applicant declares that the present invention illustrates the resin composition and its application through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photocurable resin composition, characterized in that The photocurable resin composition comprises the following components: (A) a phthalic acid diacrylate resin modified compound having a structure shown in Formula I; (B) other cationically polymerizable compounds other than the component (A); (C) a cationic photoinitiator; (D) a free radical polymerizable compound; (E) a free radical photoinitiator; Wherein, x and y are each independently selected from integers of 1 to 500; z represents an integer of 1 to 20; the weight average molecular weight of the phthalic acid diacrylate resin modified compound having the structure shown in Formula I is 5000 to 100000, and R1 and R2 each independently represent any one of a hydrogen atom, a C1 to C10 straight or branched alkyl group, a C1 to C10 alkoxy group, a C2 to C10 unsaturated hydrocarbon group, a C3 to C10 cycloalkyl group, a C2 to C10 ether group, a halogen atom or a halogenated hydrocarbon group.

2. The photocurable resin composition according to claim 1, characterized in that R1 is selected from a hydrogen atom, a C1-C2 straight-chain alkyl group, a C2-C3 ether group, a C1-C2 halogenated hydrocarbon group, and R2 is selected from a hydrogen atom or a methyl group; Preferably, 1:4≤x:y≤4:1, preferably 1:1≤x:y≤1.3:

1.

3. The photocurable resin composition according to claim 1 or 2, characterized in that: The weight average molecular weight of the phthalic acid diacrylate resin modified compound having the structure shown in Formula I is 5000 to 100000; Preferably, the x and the y are each independently selected from integers of 20-200, and z is selected from integers of 2-10.

4. The photocurable resin composition according to any one of claims 1 to 3, characterized in that The phthalic acid diacrylate resin modified compound having the structure shown in Formula I is any one of the following compounds: The definitions of x, y, and z are the same as those in claim 1.

5. The photocurable resin composition according to any one of claims 1 to 4, characterized in that Based on 100% of the total weight of the photocurable resin composition, the content of the component (A) in the photocurable resin composition is 3 to 10% by weight, more preferably 3 to 7% by weight.

6. The photocurable resin composition according to any one of claims 1 to 5, characterized in that The other cationically polymerizable compounds other than the component (A) include at least one of a cyclic ether component, a cyclic lactone component, a cyclic acetal component, a cyclic thioether component, a spirocyclic orthoester, an epoxy-functional component or an oxetane-functional component, preferably at least one of an epoxy-functional component or an oxetane-functional component, and further preferably a combination of an epoxy-functional component and an oxetane-functional component; Preferably, the epoxy-functional component comprises a compound containing an epoxycyclohexyl group and a compound containing a glycidyl group; Preferably, the epoxycyclohexyl-containing compound includes 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, adipate bis(3,4-epoxycyclohexylmethyl) ester, adipate bis(3,4-epoxy-6-methylcyclohexylmethyl) ester, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexylmethyl) ester, Any one or a combination of at least two of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate modified with β-methyl-δ-valerolactone or 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate; Preferably, the compound containing a glycidyl group includes diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol S, diglycidyl ether of brominated bisphenol A, diglycidyl ether of brominated bisphenol F, diglycidyl ether of brominated bisphenol S, diglycidyl ether of hydrogenated bisphenol A, diglycidyl ether of hydrogenated bisphenol F, diglycidyl ether of hydrogenated bisphenol S, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane ethers, diglycidyl ethers of polyethylene glycol, diglycidyl ethers of polypropylene glycol, etc.; polyglycidyl ethers of polyether polyols, which are obtained by adding one or more olefin oxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerol; diglycidyl esters of aliphatic long-chain dibasic acids; monodiglycidyl ethers of aliphatic higher alcohols; any one or a combination of at least two of phenol, cresol, butylphenol, or monodiglycidyl ethers of polyether alcohols obtained by adding olefin oxides to them, or glycidyl esters of higher fatty acids; Preferably, based on 100% of the total weight of the photocurable resin composition, the content of component (B) is 10 to 90% by weight, more preferably 50 to 70% by weight; Preferably, the cationic photoinitiator is selected from one or a combination of at least two of iodonium salt photoinitiators, sulfonium salt photoinitiators, and arylferrocenium salt photoinitiators; preferably iodonium salt photoinitiators and / or sulfonium salt photoinitiators; Preferably, the cationic photoinitiator is at least one of the compounds having a structure shown in the following formula (I) or (II): wherein R3 and R4 each independently represent hydrogen, a C1-C20 straight or branched alkyl group, a C4-C20 cycloalkylalkyl group or an alkylcycloalkyl group, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene; R5 and R6 each independently represent hydrogen, C1-C20 straight or branched alkyl, C4-C20 cycloalkylalkyl or alkylcycloalkyl, C6-C20 substituted or unsubstituted aryl, and the non-cyclic -CH2- in these groups is optionally substituted by -O-, -S- or 1,4-phenylene; R7 represents a C6-C20 substituted or unsubstituted aryl group, a C6-C20 substituted or unsubstituted alkylaryl group, a C1-C20 straight-chain or branched alkyl group, a C4-C20 cycloalkylalkyl group or an alkylcycloalkyl group, or a substituted or unsubstituted phenylthiophenyl group, and the non-cyclic -CH2- in these groups is optionally substituted by a carbonyl group, -O-, -S- or 1,4-phenylene group; R8 and R9 each independently represent an alkyl group, a hydroxyl group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an aryl group, a heterocyclic hydrocarbon group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a hydroxy(poly)alkyleneoxy group, an alkyl-substituted or unsubstituted amino group, a cyano group, a nitro group, or a halogen atom; m1 and m2 represent the number of R8 and R9, respectively, and are independently integers of 1-4; X each independently represents M-, ClO4-, CN-, HSO4-, NO3-, CF3COO-, (BM4)-, (SbM6)-, (AsM6)-, (PM6)-, Al[OC(CF3)3]4-, sulfonate ion, B(C6M5)4- or [(Rf) b PF6-b]-, wherein M is a halogen, Rf each independently represents an alkyl group in which ≥80% of hydrogen atoms are substituted by fluorine atoms, and b represents an integer of 1 to 5; Preferably, in the compounds of the structures shown in formula (I) and (II): R3 and R4 each independently represent hydrogen, C1-C12 straight chain or branched alkyl, C4-C10 cycloalkylalkyl or alkylcycloalkyl, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-; R5 and R6 each independently represent hydrogen, C1-C10 straight or branched alkyl, C4-C10 cycloalkylalkyl or alkylcycloalkyl, C6-C12 substituted or unsubstituted aryl, and the non-cyclic -CH2- in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene; R7 represents a C6-C10 substituted or unsubstituted aryl group, a C6-C10 substituted or unsubstituted alkylaryl group, or a substituted or unsubstituted phenylthiophenyl group, and the non-cyclic -CH2- in these groups may be optionally substituted by a carbonyl group, -O-, -S- or 1,4-phenylene group; R8 and R9 represent C1-C10 straight chain or branched alkyl, C1-C10 straight chain or branched alkoxy, C1-C10 alkylcarbonyl and halogen; Further preferably, the cationic part of the iodonium salt photoinitiator and / or the sulfonium salt photoinitiator comprises the following structure: Further preferably, the anion part of the iodonium salt photoinitiator or sulfonium salt photoinitiator includes Cl-, Br-, PF6-, SbF6-, AsF6-, BF4-, C4F9SO3-, B(C6H5)4-, C8F 17 SO3-, CF3SO3-, Al[OC(CF3)3]4-, (CF3CF2)2PF4-, (CF3CF2)3PF3-, [(CF3)2CF2]2PF4-, [(CF3)2CF2]3PF3-, [(CF3)2CFCF2]2PF4- or (CF3)2CFCF2]3PF3-; Based on 100% of the total weight of the photocurable resin composition, the content of the component (C) is 0.1 to 10% by weight.

7. The photocurable resin composition according to any one of claims 1 to 6, characterized in that The free radical polymerizable compound includes a monofunctional ethylenically unsaturated component and / or a multifunctional ethylenically unsaturated component; Preferably, the monofunctional ethylenically unsaturated component comprises acrylamide, N,N-dimethylacrylamide, (meth)acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth)acrylate, isobutoxymethyl (meth)acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl diethylene glycol (meth)acrylate, tert-octyl (meth)acrylamide, diacetone (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, lauryl (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, N,N-dimethyl (meth)acrylamide, tetramethyl (meth)acrylate, tetramethyl Any one or a combination of at least two of chlorophenyl ester, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, N-vinyl pyrrolidone, phenoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, bornyl (meth)acrylate or methyl triethylene glycol (meth)acrylate; Preferably, examples of the multifunctional ethylenically unsaturated component include ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tricyclodecane diyl dimethylene di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, tripropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, dicapped (meth)acrylic acid addition product of bisphenol A diglycidyl ether, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, Any one of polyethylene glycol di(meth)acrylate, a pentaerythritol derivative with a (meth)acrylate functional group (for example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate or dipentaerythritol tetra(meth)acrylate), di(trimethylolpropane) tetra(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated modified hydrogenated bisphenol A di(meth)acrylate or ethoxylated bisphenol F di(meth)acrylate, or a combination of at least two thereof; Preferably, based on 100% of the total weight of the photocurable resin composition, the content of component (D) is 5 to 60% by weight; Preferably, examples of the free radical photoinitiator include any one or a combination of at least two of benzophenones, benzoins, acetophenones, benzil, benzil ketal, anthraquinones, triphenylphosphine; benzoylphosphine oxides, thioxanthones and tonones, acridine derivatives, phenazine derivatives, quinoline derivatives, 1-phenyl-1,2-propanedione-2-O-benzoyl oxime, 1-aminobenzophenones, 1-hydroxybenzophenones or triazine compound initiators. Preferably, based on the total weight of the photocurable resin composition as 100%, the content of the component (E) is 0.01-15% by weight, preferably 0.1-15% by weight, and further preferably 1-10% by weight; Preferably, the photocurable resin composition further comprises other conventional additives; Preferably, the other conventional additives include any one or a combination of at least two of stabilizers, tougheners, fillers, dyes, pigments, antioxidants, wetting agents, defoamers, chain transfer agents, thickeners, leveling agents, defoamers, UV absorbers or surfactants.

8. A three-dimensional product, characterized in that The three-dimensional article is prepared from the photocurable resin composition according to any one of claims 1 to 7.

9. Use of the photocurable resin composition according to any one of claims 1 to 7 in stereolithography or three-dimensional inkjet printing.

10. Use of the photocurable resin composition according to any one of claims 1 to 7 or the three-dimensional product according to claim 8 in aerospace industry materials, medical supplies, coatings or light emitting diode materials.

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