Photocurable composition, application of photocurable composition in 3D printing and 3D printed product

Abstract

The invention relates to a photocurable composition, an application of the photocurable composition in 3D printing, especially SLA 3D printing, and a 3D printing product obtained from the photocurable composition. The photocurable composition provided by the invention has good curing performance and can be used for preparing a product with a larger size and a complex fine structure, and the obtained printed product has good mechanical performance and good appearance.

Description

Technical Field

[0001] The present invention relates to a photocurable composition and use thereof in 3D printing, in particular SLA 3D printing, and a 3D printed product obtained from the photocurable composition. Background Art

[0002] 3D printing technology, also known as additive manufacturing, originated in the 1980s and has now developed into an extremely important material manufacturing method. Compared with traditional processing methods, 3D printing does not require the use of molds, avoiding mechanical processing and subtractive manufacturing methods. In addition, 3D printing is controlled by a computer, which gives it excellent precision and the ability to manufacture complex and precise structures. In recent years, 3D printing technology based on photocuring has attracted much attention, which is attributed to the "green" characteristics of photocuring technology, such as energy saving, environmental protection, and high efficiency. Therefore, research on photocuring 3D printing has been widely reported. These methods usually have advantages such as mild processing conditions, nearly 100% material utilization, and high production efficiency, which enable them to be widely used.

[0003] Since commercially available photoinitiators, such as acylphosphine oxides or thioxanthones, are photosensitized to short-wavelength light, such as near-ultraviolet light and blue light, short-wavelength light is often used as the main light source for photocuring 3D printing. However, in recent years, the use of long-wavelength light as a light source has become an important research direction in the field of photocuring. After all, short-wavelength light is not good for human health, and its limited penetration ability is not conducive to deep curing. Based on this, photocuring technology using near-infrared light (NIR, wavelength greater than 700nm) as a light source has emerged. This is because near-infrared light is safer for the human body than ultraviolet light, which is extremely important for health issues in actual production processes.

[0004] At present, relevant articles on near-infrared light-curing 3D printing have been reported. For example, 3D printing based on upconversion nanoparticles (UCNPs) direct ink writing (DIW) (Nat Commun 2020, 11, 3462), which can even manufacture ceramic products under NIR light source irradiation (Nat Commun 2023, 14, 2381). However, the preparation process of UCNPs is complicated and the cost is high, which reduces its practical applicability.

[0005] Stereolithography (SLA) 3D printing technology has the characteristics of fast processing speed and high precision. At the same time, compared with the above-mentioned DIW and DLP methods, SLA 3D printing has advantages in preparing large-sized and complex precision products. However, the current photocurable compositions are not printable enough when used for 3D printing, especially SLA 3D printing. Even if they can be printed, the performance of the resulting products is poor. Therefore, it is of great significance to develop a photocurable composition that can be used for 3D printing, especially SLA 3D printing. Summary of the invention

[0006] In view of the problems existing in the prior art, the inventors have conducted in-depth research on photocurable compositions suitable for near-infrared light sources. The inventors surprisingly found that the photocurable composition of the present invention is suitable for 3D printing, especially SLA 3D printing, has good photocuring performance and the resulting printed products have good and stable mechanical properties. The photocurable composition of the present invention may also contain a colorant and be used to prepare colored products; the photocurable composition of the present invention can prepare products of larger size and containing complex fine structures (such as hollow structures), which are difficult to prepare with existing near-infrared photocurable compositions.

[0007] An object of the present invention is to provide a photocurable composition.

[0008] Another object of the present invention is to provide a photocurable composition for use in 3D printing, especially SLA 3D printing.

[0009] Another object of the present invention is to provide a photocured product obtained from the photocurable composition of the present invention.

[0010] The technical solution for achieving the purpose of the present invention can be summarized as follows:

[0011] 1. A photocurable composition comprising the following components:

[0012] (a) at least one polymethine cyanine compound as an infrared absorbing photosensitizer;

[0013] (b) at least one photopolymerization initiator;

[0014] (c) at least one free radical photopolymerizable compound;

[0015] (d) at least one electron donating reducing agent; and

[0016] (e) at least one aryl phosphorus compound.

[0017] 2. The photocurable composition according to embodiment 1, wherein the polymethine cyanine compound as component (a) has a structure represented by formula (I):

[0018]

[0019] in

[0020] Y + represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members and having a positive charge,

[0021] Y represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members,

[0022] Y + The heterocyclic ring in the definition of Y may contain one or more selected from halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 branched or unbranched alkylthio or phenylthio substituents, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms;

[0023] Preferred Y + / Y are the structural units shown below:

[0024] Indole Salt / Indole

[0025] Phenyl[e]indole salt / phenyl[e]indole

[0026] and / or phenyl[c,d]indole salts / phenyl[c,d]indole,

[0027] The benzene ring or naphthalene ring of the indole salt / indole, phenyl[e]indole salt / phenyl[e]indole, and phenyl[c,d]indole salt / phenyl[c,d]indole may have one or more, preferably one or two, selected from halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 branched or unbranched alkylthio or phenylthio substituents, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-

[0028] C12 The alkyl group in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms; wherein R1 is selected from C1-C 12 Branched or unbranched alkyl and C1-C 12 A branched or unbranched alkoxy group, wherein the C1-C 12 Branched or unbranched alkyl and C1-C 12 Branched or unbranched alkoxy groups may be interrupted by one or more non-adjacent oxygen atoms, such as –[-CH2CHR-O-] n The polyether shown, wherein n is 1-6, and R is H or CH3;

[0029] The ring carbon position indicated by the arrow is the connection site with the polymethine chain;

[0030] More preferably Y + / Y are the structural units shown below:

[0031]

[0032] and / or

[0033] Wherein R1 is selected from C1-C 12 Branched or unbranched alkyl and C1-C 12 A branched or unbranched alkoxy group, wherein the C1-C 12 Branched or unbranched alkyl and C1-C 12 Branched or unbranched alkoxy groups may be interrupted by one or more non-adjacent oxygen atoms, such as –[-CH2CHR-O-] n The polyether shown, wherein n is 1-6, and R is H or CH3; and

[0034] R2, R3 are independently selected from H, halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 A branched or unbranched alkylthio or phenylthio group, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms;

[0035] The ring carbon position indicated by the arrow is the connection site with the polymethine chain;

[0036] n1, n2 are independently 0, 1 or 2; preferably 0 or 1, more preferably 1;

[0037] B and C are independently selected from H, Cl-C12 Alkyl groups may form a five-membered ring or a six-membered ring together with the carbon atoms to which they are attached;

[0038] A is selected from the structures shown in A-1 to A-13:

[0039]

[0040] or C1-C 12 Branched or unbranched alkoxy group (A-13);

[0041] in

[0042] * represents the connection site with the structure of formula (I),

[0043] wherein the "R2 and R2" groups are identical or different and are each independently selected from hydrogen, halogen, C1-C6 branched or unbranched alkyl, C1-C6 branched or unbranched alkoxy, C1-C6 branched or unbranched alkylthio or phenylthio,

[0044] Preferably, group A is selected from the structures shown in A-1, A-2, A-4, A-5 or A-7 to A-13;

[0045] When the A group is a group A-1 or A-2, n3 is 0, and when the A group is one of the groups A-3 to A-13, n3 is 1,

[0046] and X - represents the counter ion.

[0047] 3. The photocurable composition according to embodiment 2, wherein the compound of formula (I) satisfies one or more of the following conditions:

[0048] R1 is selected from C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms;

[0049] R2 is selected from H, halogen, nitro, C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl, the C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms;

[0050] R3 is selected from H, C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl and the C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms.

[0051] 4. The photocurable composition according to embodiment 2 or 3, wherein B and C are independently H or form a five-membered ring or a six-membered ring together with the carbon atoms to which they are connected, preferably B and C form a five-membered ring or a six-membered ring together with the carbon atoms to which they are connected.

[0052] 5. The photocurable composition according to any one of items 2 to 4, wherein the "R2 and R2" groups are the same or different and are each independently selected from hydrogen or a C1-C6 branched or unbranched alkyl group.

[0053] 6. The photocurable composition according to any one of embodiments 2 to 5, wherein X - Represents the following counter ions: BF4 - , [B(Ph4] - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - , Cl - Br - 、F - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - 、[C(O-SO2CF3)3] - 、[nC 12 H 25- TsO - or [NTf2] - , among which BF4 is preferred - , [B(Ph4] - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - 、[Al(Ot-C4F9)4] -、[Al(O-(i-C3F7)CH3)4] - or [NTf2] - .

[0054] 7. The photocurable composition according to any one of embodiments 2 to 6, wherein the polymethine cyanine compound as component (a) is selected from one or more of compounds S1 to S189 as defined herein;

[0055] Preferably, the polymethine anthocyanin compound as component (a) is selected from S132, S44 or a mixture thereof.

[0056] 8. The photocurable composition according to any one of embodiments 1 to 7, wherein the photopolymerization initiator as component (b) is a photopolymerization initiator capable of generating free radicals in the presence of component (a).

[0057] 9. The photocurable composition according to any one of embodiments 1 to 8, wherein the photopolymerization initiator as component (b) is selected from iodonium salts, sulfonium salts, triazines and oxime ester-based photopolymerization initiators.

[0058] 10. The photocurable composition according to any one of embodiments 1 to 9, wherein the photopolymerization initiator as component (b) is an iodonium salt, preferably selected from iodonium salts represented by formula II:

[0059]

[0060] Wherein, R1'-R6' may be the same or different and independently selected from H, halogen, nitro, C1-C 20 Branched or unbranched alkyl, C1-C 20 Branched or unbranched alkoxy and C1-C 20 Branched or unbranched alkylthio, and X' - For example, in Embodiment 2 or 6, X in the compound of formula (I) - As defined,

[0061] Preferably, X in the compound of formula (I) is - and X' in the compound of formula (II) - are the same.

[0062] 11. The photocurable composition according to any one of embodiments 1 to 10, wherein the photopolymerization initiator as component (b) is selected from one or more of the compounds IS1 to IS41 as defined herein;

[0063] It is preferred that the photopolymerization initiator as component (b) is selected from IS1, IS41 or a mixture thereof.

[0064] 12. The photocurable composition according to any one of embodiments 1 to 11, wherein the weight ratio of the infrared absorbing photosensitizer as component (a) to the photopolymerization initiator as component (b) is 100:1-1:100, preferably 1:1-1:100, more preferably 1:10-1:100.

[0065] 13. The photocurable composition according to any one of embodiments 1 to 12, wherein the amount of the infrared absorbing photosensitizer as component (a) is 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on the total weight of the photocurable composition.

[0066] 14. The photocurable composition according to any one of embodiments 1 to 13, wherein the amount of the photopolymerization initiator as component (b) is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the photocurable composition.

[0067] 15. A photocurable composition according to any one of embodiments 1 to 14, wherein the free radical photopolymerizable compound contains at least one of a free radical polymerizable resin, a free radical polymerizable monomer with two or more functional groups, and a monofunctional free radical polymerizable monomer, preferably the free radical photopolymerizable compound contains a free radical polymerizable resin and a free radical polymerizable monomer with two or more functional groups, or the free radical photopolymerizable compound contains a free radical polymerizable resin and a monofunctional free radical polymerizable monomer, or the free radical photopolymerizable compound contains a free radical polymerizable resin, a free radical polymerizable monomer with two or more functional groups, and a monofunctional free radical polymerizable monomer.

[0068] 16. The photocurable composition according to any one of embodiments 1 to 15, wherein the electron donating reducing agent is selected from phenylglycine compounds and aryl borate salts, preferably from phenylglycine compounds and aryl borate salts, for example from sodium tetraphenylborate and N-phenylglycine.

[0069] 17. The photocurable composition according to any one of embodiments 1 to 16, wherein the weight ratio of the electron donating reducing agent to the photopolymerization initiator is 5:1-1:50, preferably 1:1-1:40, and more preferably 1:2-1:20.

[0070] 18. The photocurable composition according to any one of embodiments 1 to 17, wherein the amount of the electron donating reducing agent is 0.05-2 wt %, preferably 0.08-1.2 wt %, based on the total weight of the photocurable composition.

[0071] 19. The photocurable composition according to any one of embodiments 1 to 18, wherein the aryl phosphorus compound is an aryl phosphorus compound having a trivalent phosphorus atom, especially triphenylphosphine.

[0072] 20. The photocurable composition according to any one of embodiments 1 to 19, wherein the weight ratio of the aryl phosphorus compound to the photopolymerization initiator is 5:1-1:50, preferably 1:1-1:40, and more preferably 1:2-1:20.

[0073] 21. The photocurable composition according to any one of embodiments 1 to 20, wherein the weight ratio of the electron donating reducing agent to the aryl phosphorus compound is 10:1-1:10, preferably 5:1-1:5, more preferably 3:1-1:3.

[0074] 22. The photocurable composition according to any one of embodiments 1 to 21, wherein the amount of the aryl phosphorus compound is 0.05-2% by weight, preferably 0.08-1.2% by weight, based on the total weight of the photocurable composition.

[0075] 23. A photocurable composition according to any one of embodiments 1 to 22, wherein the photocurable composition comprises at least one colorant, such as a dye and a pigment, in particular the amount of the colorant is 0.05-20 wt %, preferably 0.08-10 wt % or 0.1-2 wt %, based on the total weight of the photocurable composition.

[0076] 24. Use of the photocurable composition of any one of embodiments 1 to 23 in 3D printing, especially SLA 3D printing, preferably using a NIR (laser) light source with an emission wavelength of 700-2000nm, preferably 750-900nm to process the photocurable composition.

[0077] 25. A photocured product obtained from the photocurable composition according to any one of embodiments 1 to 23.

[0078] The photocurable composition of the present invention has excellent absorption performance in the near-infrared light region, can be cured under irradiation with relatively low light intensity, and the initiator system used for the photocurable composition can undergo photolysis reaction under irradiation with near-infrared light; the photocurable composition has good curing performance, such as a faster polymerization rate and a high curing rate, and has good curing performance even after adding a colorant. The photocurable composition of the present invention also has good thermal stability. The photocurable composition of the present invention can be used to successfully realize SLA 3D printing, and can prepare larger-sized products containing complex fine structures (such as hollow structures), and the resulting printed products have good and stable mechanical properties and good appearance. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1 is the light absorption curve of the photocurable composition of Example 1;

[0080] Figure 2 is the light absorption curve of the photocurable composition of Example 2;

[0081] Figure 3 and Figure 4 is a polymerization curing rate curve and a polymerization rate curve of the photocurable composition of Example 3 under 808 nm NIR laser light source irradiation;

[0082] Figure 5 and Figure 6 is a polymerization curing rate curve and a polymerization rate curve of the photocurable composition of Example 4 under 808 nm NIR laser light source irradiation;

[0083] Figure 7 and Figure 8 is a polymerization curing rate curve and a polymerization rate curve of the photocurable composition of Example 5 under 808 nm NIR laser light source irradiation;

[0084] Fig. 9 and Fig.10 is a polymerization curing rate curve and a polymerization rate curve of the photocurable composition of Example 6 under 808 nm NIR laser light source irradiation;

[0085] Fig.11 is a temperature versus heat flow rate curve obtained by DSC testing of the photocurable composition of Example 7;

[0086] Fig.12 is a temperature versus heat flow rate curve obtained by DSC testing of the photocurable composition of Example 8;

[0087] FIG. 13( a ) is a product display diagram of the photocurable composition of Example 9 prepared by a 3D printer, and FIG. 13( b ) is a stretch rod prepared in Example 15;

[0088] Fig.14 This is a product display diagram of the photocurable composition of Example 10 prepared by 3D printer processing;

[0089] Fig.15 This is a product display diagram of the photocurable composition of Example 11 prepared by 3D printer processing;

[0090] Fig.16 This is a product display diagram of the photocurable composition of Example 12 prepared by a 3D printer;

[0091] Fig.17 is the photodegradation curve of the photocurable composition of Example 13 under 820 nm NIR laser light source irradiation;

[0092] Fig.18: is the photodegradation curve of the photocurable composition of Example 14 under 820 nm NIR laser light source irradiation.

[0093] Fig.19 This is the stress-strain curve of the product prepared by the photocurable composition of Example 15 through 3D printer processing. DETAILED DESCRIPTION

[0094] Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not necessary except for the cases specifically indicated. The same is true for numerical values ​​and their ranges, and the present invention is not limited thereto.

[0095] As used herein, “(meth)acrylic acid” refers to acrylic acid or methacrylic acid, “(meth)acrylate” refers to acrylate or methacrylate, and “(meth)acryloyl” refers to acryloyl or methacryloyl.

[0096] In addition, herein, the use of a numerical range indicates a range in which the numerical values ​​described before and after are respectively the minimum value and the maximum value.

[0097] Specific values ​​disclosed herein for related features (including the end points of the ranges) can be combined with each other to form a new range.

[0098] In the present invention, the prefix "C n -C m " in each case means that the number of carbon atoms contained in the group is nm.

[0099] "Halogen" refers to fluorine, chlorine, bromine and iodine. In the present invention, preferably, halogen includes F, Cl or a combination thereof. "Halo" refers to substitution by one or more halogen atoms which may be the same or different.

[0100] As used herein, the term “C n -C m Alkyl" and "C n -C mThe term "unbranched or branched alkyl" refers to a branched or unbranched saturated hydrocarbon radical having, for example, 1 to 20, preferably 1 to 12, more preferably 1 to 8, particularly preferably 1 to 6, such as 1 to 5 or 1 to 4, carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- Dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl and isomers thereof. C1-C8 alkyl can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl and isomers thereof. C1-C6 alkyl can be methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, tert-butyl, pentyl, isopentyl, hexyl and isomers thereof. C1-C4 alkyl can be methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl and isomers thereof.

[0101] The term "C2-C mThe term "alkenyl" refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, for example 2 to 20 or 2 to 12, preferably 2 to 6, more preferably 2 to 4 carbon atoms and having one double bond located in any position, such as vinyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl The C2-C6 alkenyl group may be vinyl, propenyl, 1-butenyl, 2-butenyl, isobutenyl, 1-pentenyl, 2-pentenyl, neopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, isohexenyl, neohexenyl and isomers thereof.The C2-C4 alkenyl group may be ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl and isomers thereof.

[0102] The term "C3-C m "Cycloalkyl" refers to a saturated alicyclic monocyclic group having 3-m, for example 3-20, preferably 3-8, more preferably 5-6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.

[0103] The term "C n -C m Alkoxy" and "C n -C m "Alkylthio" refers to a C n -C m Alkyl corresponding to the open chain C n -C m Any carbon atom of an alkane is bonded with an oxygen atom or a sulfur atom as a linking group. n -C m Alkyl, such as C1-C 20 Alkoxy (or thio) group, preferably C1-C 12 Alkoxy (or thio) group, more preferably C1-C8 alkoxy (or thio) group, particularly preferably C1-C6 alkoxy (or thio) group, especially preferably C1-C4 alkoxy (or thio) group. C1-C8 alkoxy group can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy and isomers thereof. C1-C4 alkoxy group can be methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy and isomers thereof. C1-C8 alkylthio group can be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, 2-butylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, isooctylthio and isomers thereof. The C1-C4 alkylthio group may be methylthio, ethylthio, propylthio, isopropylthio, n-butylthio and isomers thereof.

[0104] Y + , Y mentioned bicyclic, tricyclic or more heterocyclic rings having 8-18 ring members and containing 1 or 2 nitrogen atoms as ring members, preferably bicyclic or tricyclic heterocyclic rings having 8-14 ring members and containing 1 nitrogen atom as a ring member.

[0105] Photocurable composition

[0106] The first aspect of the present disclosure relates to a photocurable composition comprising the following components:

[0107] (a) at least one polymethine cyanine compound as an infrared absorbing photosensitizer;

[0108] (b) at least one photopolymerization initiator;

[0109] (c) at least one free radical photopolymerizable compound;

[0110] (d) at least one electron donating reducing agent; and

[0111] (e) at least one aryl phosphorus compound.

[0112] The photocurable composition according to the present invention is particularly suitable for near-infrared light curing. In a preferred embodiment, the photocurable composition is a free radical polymerizable near-infrared light curable composition. Component (a): a polymethine anthocyanin compound as an infrared absorbing photosensitizer

[0113] In a preferred embodiment, the polymethine anthocyanin compound as component (a) is selected from polymethine anthocyanin compounds having the structure of formula (I):

[0114]

[0115] Y + represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members and having a positive charge,

[0116] Y represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members,

[0117] Y + The heterocyclic ring defined in and Y may contain one or more selected from halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 branched or unbranched alkylthio or phenylthio substituents, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms;

[0118] Preferred Y + / Y are the structural units shown below:

[0119] Indole Salt / Indole

[0120] Phenyl[e]indole salt / phenyl[e]indole

[0121] and / or phenyl[c,d]indole salts / phenyl[c,d]indole,

[0122] The benzene ring or naphthalene ring of the indole salt / indole, phenyl[e]indole salt / phenyl[e]indole, and phenyl[c,d]indole salt / phenyl[c,d]indole may have one or more, preferably one or two, selected from halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 branched or unbranched alkylthio or phenylthio substituents, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-

[0123] C 12 The alkyl group in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms; wherein R1 is selected from C1-C 12 Branched or unbranched alkyl and C1-C 12 A branched or unbranched alkoxy group, wherein the C1-C 12 Branched or unbranched alkyl and C1-C 12 Branched or unbranched alkoxy groups may be interrupted by one or more non-adjacent oxygen atoms, such as –[-CH2CHR-O-] n The polyether shown, wherein n is 1-6, and R is H or CH3;

[0124] The ring carbon position indicated by the arrow is the connection site with the polymethine chain;

[0125] More preferably Y + / Y are the structural units shown below:

[0126]

[0127] and / or

[0128] Wherein R1 is selected from C1-C 12 Branched or unbranched alkyl and C1-C 12 A branched or unbranched alkoxy group, wherein the C1-C 12 Branched or unbranched alkyl and C1-C 12Branched or unbranched alkoxy groups may be interrupted by one or more non-adjacent oxygen atoms, such as –[-CH2CHR-O-] n The polyether shown, wherein n is 1-6, and R is H or CH3; and

[0129] R2, R3 are independently selected from H, halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 A branched or unbranched alkylthio or phenylthio group, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms;

[0130] The ring carbon position indicated by the arrow is the connection site with the polymethine chain;

[0131] n1, n2 are independently 0, 1 or 2; preferably 0 or 1, more preferably 1;

[0132] B and C are independently selected from H, Cl-C 12 Alkyl groups may form a five-membered ring or a six-membered ring together with the carbon atoms to which they are attached;

[0133] A is selected from the structures shown in A-1 to A-13:

[0134]

[0135] or C1-C 12 Branched or unbranched alkoxy group (A-13);

[0136] in

[0137] * represents the connection site with the structure of formula (I),

[0138] wherein the "R2 and R2" groups are identical or different and are each independently selected from hydrogen, halogen, C1-C6 branched or unbranched alkyl, C1-C6 branched or unbranched alkoxy, C1-C6 branched or unbranched alkylthio or phenylthio,

[0139] Preferably, group A is selected from the structures shown in A-1, A-2, A-4, A-5 or A-7 to A-13;

[0140] When the A group is a group A-1 or A-2, n3 is 0, and when the A group is one of the groups A-3 to A-13, n3 is 1,

[0141] and X - represents the counter ion.

[0142] In one embodiment, R1 is selected from C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms.

[0143] In one embodiment, R2 is selected from H, halogen, nitro, C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl, the C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms, more preferably R2 is selected from H, halogen, nitro and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkoxy may be interrupted by 1 non-adjacent oxygen atom.

[0144] In one embodiment, R3 is selected from H, C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl and the C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms, more preferably R3 is selected from H and C1-C6 branched or unbranched alkoxy.

[0145] In one embodiment, B and C are independently H or form a five-membered ring or a six-membered ring together with the carbon atoms connecting them. In one embodiment, B and C form a five-membered ring or a six-membered ring together with the carbon atoms connecting them. In a preferred embodiment, the five-membered ring or the six-membered ring has only one carbon-carbon unsaturated double bond.

[0146] In one embodiment, the "R2 and R2" groups are the same or different and are each independently selected from hydrogen or C1-C6 branched or unbranched alkyl, preferably hydrogen or C1-C6 branched or unbranched alkyl. In one embodiment, the "R2 and R2" groups are the same or different and are each independently C1-C6 branched or unbranched alkyl.

[0147] In one embodiment, X - represents a counter ion selected from the group consisting of: BF4 - , [B(Ph4] - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N]- 、[((CF3)2SO2)3C] - , Cl - Br - 、F - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - 、[C(O-SO2CF3)3] - 、[nC 12 H 25- TsO - or [NTf2] - ,

[0148] Among them, BF4 is preferred - , [B(Ph4] - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - or [NTf2] - ,

[0149] More preferably [PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(Ph4] - PF6 - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - 、[Al(Ot-C4F9)4] - or [Al(O-(i-C3F7)CH3)4] - .

[0150] In the compound of formula (I), when the A group is A-1 or A-2 and Y + and R1 in Y is C1-C 12Branched or unbranched alkyl or C1-C 12 In the case of branched or unbranched alkoxy, the structure of formula (I) is uncharged as a whole, X is absent, and when R 2 When the group is one of the groups A-3 to A-13, the structure of formula (I-1) is positively charged as a whole:

[0151]

[0152] where Y + , Y, A, B, C, n1, n2 are as defined above.

[0153] In the compound of formula (I), when A is selected from A-1 or A-2, X is absent, ie n3 is 0.

[0154] When A is selected from one of A-3 to A-13, the structure of formula (I-1) has a positive charge as a whole, X - As defined above, n3 is 1.

[0155] In the present invention, the polymethine anthocyanin compound of formula (I) comprises a structural moiety of formula (I-1) and, if present, a counterion X - .

[0156]

[0157] In the polymethine anthocyanin compound of formula (I) of the present invention and the structural part of formula (I-1) contained therein, n1 and n2 are independently 0, 1 or 2, and n3 is independently 0 or 1. B and C independently represent H, C1-C 12 Alkyl or together with the carbon atoms connecting them form a five-membered ring or a six-membered ring. When n1 and n2 are both 0, the compound of formula (I) is a trimethine compound, when n1 is 0 and n2 is 1, the compound of formula (I) is a pentamethine compound, when n1 and n2 are 1, the compound of formula (I) is a heptamethine compound, when n1 and n2 are 1, and B, C together with the carbon atoms connecting them form a five-membered ring, or a six-membered ring, the compound of formula (I) is a heptamethine compound containing a five-membered ring or a six-membered ring in the middle position. In a preferred embodiment of the present invention, the compound of formula (I) is a trimethine compound, wherein n1 and n2 are both 0. In another preferred embodiment of the present invention, the compound of formula (I) is a pentamethine compound, wherein n1 is 0 and n2 is 1. In another preferred embodiment of the present invention, the compound of formula (I) is a heptamethine compound in which B, C and the carbon atoms connecting them form a five-membered ring, wherein n1 and n2 are 1.

[0158] In the polymethine anthocyanin compound of formula (I) of the present invention, (X - ) n3If present, it represents the counterion of the moiety of formula (I-1) and, depending on the type of group A, is either not present at all or is anionic.

[0159] When the structural part of formula (I-1) is uncharged as a whole, n3 is 0, that is, the compound of formula (I) does not have any counter ions.

[0160] In one embodiment of the present invention, in the polymethine anthocyanin compound of formula (I) of the present invention and the structural part of formula (I-1) contained therein, Y + and Y both contain a nitrogen-containing heterocyclic ring, Y + The difference from the structure of Y is that + The included nitrogen ring atoms have a positive charge, while Y does not exhibit any charge.

[0161] Advantageously, the A group is A-1, A-4, A-5 or A-7 to A-13, or the A group is A-1, A-4, A-5, A-7, A-8, A-11, A-12 or A-13.

[0162] The preferred cyanine dye structural formulas can be divided into the following four groups: S-1, S-2, S-3 and S-4:

[0163]

[0164] Where A, R1, R2, R3, m and X - As defined above, m is 0-2 (eg, 0, 1, and 2), and n is 0 or 1.

[0165] In one embodiment, the polymethine anthocyanin compound as component (a) is selected from one or more of the following compounds S1-S189:

[0166]

[0167] When n=0, it is a five-membered ring, and when n=1, it is a six-membered ring;

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174] Wherein barb1 refers to the A-1 group as defined above in which "R2 and R2" are both -CH3, and barb2 refers to the A-2 group as defined above in which "R2 and R2" are both -CH3, i.e.

[0175]

[0176] The compound of formula (I) of the present invention is known from, for example, JP-A-2010-209191, or can be prepared by a conventional method in the art.

[0177] Preferably, the polymethine anthocyanin compound as component (a) is selected from S132, S44 or a mixture thereof.

[0178] According to the present invention, the amount of the infrared absorbing photosensitizer as component (a) can be 0.001-5% by weight, such as 0.002% by weight, 0.005% by weight, 0.008% by weight, 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight or 4.8% by weight, preferably 0.005-4% by weight, 0.01-3% by weight, 0.01-2% by weight, 0.01-1% by weight, 0.02-0.8% by weight, or 0.02-0.5% by weight.

[0179] Component (b): Photopolymerization initiator

[0180] According to one embodiment of the present invention, the photopolymerization initiator as component (b) can be a photopolymerization initiator capable of generating free radicals in the presence of component (a). Preferably, the photopolymerization initiator as component (b) is selected from the group consisting of iodonium salt compounds, sulfonium salt compounds, triazine compounds and oxime ester compounds, preferably iodonium salt compounds.

[0181] As the iodonium salt compound suitable for the present invention, the iodonium salt compound including the formula (II) is preferred.

[0182]

[0183] Wherein, R1'-R6' may be the same or different and are independently selected from H, halogen, nitro, C1-C 20 Branched or unbranched alkyl, C1-C 20 Branched or unbranched alkoxy and C1-C 20Branched or unbranched alkylthio, and X' - As above for X in the compound of formula (I) - In one embodiment, R1'-R6' may be the same or different and are independently selected from H, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy and C1-C 12 In one embodiment, R1'-R6' may be the same or different and are independently selected from H and C1-C 12 In one embodiment, R1', R3', R4' and R6' are H, R2' and R5' are C1-C 12 Branched or unbranched alkyl, preferably C1-C6 branched or unbranched alkyl, especially methyl.

[0184] In one embodiment, X in the compound of formula (I) - With X' in the compound of formula (II) - are the same.

[0185] The iodonium salt of formula (II) of the present invention is known per se and can be prepared by conventional methods in the art.

[0186] In an advantageous embodiment of the present invention, the iodonium salt initiator of formula (II) as component (b) is one or more selected from the following compounds IS1-IS41:

[0187]

[0188]

[0189]

[0190] It is preferred that the photopolymerization initiator as component (b) is selected from IS1, IS41 or a mixture thereof.

[0191] The amount of the photopolymerization initiator as component (b) can be 0.1-10 wt %, such as 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.2 wt %, 1.5 wt %, 1.8 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt %, 5.5 wt %, 6 wt %, 6.5 wt %, 7 wt %, 7.5 wt %, 8 wt %, 8.5 wt %, 9 wt %, 9.5 wt %, preferably 0.5-8 wt % or 0.5-5 wt %, based on the total weight of the photocurable composition.

[0192] In one embodiment, the weight ratio of the infrared absorbing photosensitizer as component (a) to the photopolymerization initiator as component (b) is 100:1-1:100 (e.g., 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 8:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:8, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80 or 1:90), preferably 10:1-1:100 or 1:1-1:100, more preferably 1:10-1:100. Component (c): free radical photopolymerizable compound

[0193] According to a preferred embodiment of the present invention, the free radical photopolymerizable compound (c) is a free radical polymerizable compound containing an ethylenically unsaturated group, in particular a compound containing a free radical polymerizable unsaturated carbon-carbon double bond. The free radical polymerizable compound may be in the form of a monomer and / or a resin (including an oligomer or a prepolymer).

[0194] In one embodiment, the amount of the free radical photopolymerizable compound as component (c) can be 50-98.5 wt % (e.g., 55 wt %, 60 wt %, 65 wt %, 70 wt %, 75 wt %, 80 wt %, 85 wt %, 90 wt %, 95 wt %, 96 wt %, 97 wt %, 97.1 wt %, 97.2 wt %, 97.3 wt %, 97.5 wt %, 97.6 wt %, 97.7 wt %, 97.8 wt %, 97.9 wt %, 98 wt %, 98.1 wt %, 98.2 wt %, 98.3 wt % or 98.4 wt %), preferably 60-98.5 wt %, 70-98.5 wt % or 70-98.3 wt %, 80-98.5 wt %, 80-98.2 wt %, 85-98 wt % or 90-98 wt %, based on the total weight of the photocurable composition.

[0195] In one embodiment, the free radical photopolymerizable compound comprises a free radical polymerizable monomer and a free radical polymerizable resin. The weight ratio of the free radical polymerizable monomer to the free radical polymerizable resin can be 15:1-1:10 (e.g., 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9), preferably 12:1-1:5, more preferably 10:1-1:1 or 8:1-2:1.

[0196] In one embodiment, the free radical polymerizable monomer (especially monofunctional and / or difunctional compound) can be 10-85 weight % (such as 15 weight %, 20 weight %, 30 weight %, 40 weight %, 50 weight %, 60 weight %, 70 weight %, 80 weight % or 82 weight %), preferably 20-82 weight %, 30-82 weight %, 40-80 weight %, or 50-80 weight % based on the total weight of the photocurable composition of the present invention.

[0197] In one embodiment, the amount of the free radical polymerizable resin can be 12-80 wt %, such as 15 wt %, 20 wt %, 25 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %, 70 wt %, preferably 15-75 wt % or 15-60 wt % or 15-45 wt %, based on the total weight of the photocurable composition.

[0198] In one embodiment, the free radical photopolymerizable compound contains at least one of a free radical polymerizable resin, a free radical polymerizable monomer with two or more functional groups, and a monofunctional free radical polymerizable monomer. Preferably, the free radical photopolymerizable compound contains a free radical polymerizable resin and a free radical polymerizable monomer with two or more functional groups, or the free radical photopolymerizable compound contains a free radical polymerizable resin and a monofunctional free radical polymerizable monomer, or the free radical photopolymerizable compound contains a free radical polymerizable resin, a free radical polymerizable monomer with two or more functional groups, and a monofunctional free radical polymerizable monomer.

[0199] Free radical polymerizable monofunctional compound (monomer)

[0200] The free radical polymerizable monofunctional compound has low viscosity and can be used as a photoreactive diluent, and examples thereof include (meth)acrylate compounds, (meth)acryloyl compounds, vinyl derivatives, styrene compounds, anhydride compounds containing ethylenically unsaturated double bonds (maleic anhydride), N-vinylformamide, and monofunctional compounds with a cyclic structure, such as N-vinylpyrrolidone and acryloylmorpholine, etc. In a preferred embodiment, the free radical polymerizable monomer comprises a monofunctional compound with a cyclic structure, such as N-vinylpyrrolidone and acryloylmorpholine, etc.

[0201] As the (meth)acrylate compounds, the following examples may preferably be mentioned:

[0202] (Meth) acrylic acid C1-C 18 Alkyl esters, such as (meth) acrylic acid C1-C 12Alkyl esters or C1-C6 alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl acrylate (2-EHA), isodecyl acrylate (IDA), lauryl (meth)acrylate, stearyl (meth)acrylate, 2-methacryloylethoxyphthalate;

[0203] Hydroxy-functional (meth)acrylates, such as hydroxy C1-C6 alkyl (meth)acrylates, examples being 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycidyl methacrylate and the like (meth)acrylates;

[0204] (Meth)acrylates having a cyclic skeleton, such as isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, γ-butyrolactone (meth)acrylate, γ-butyrolactone (meth)acrylate, tricyclodecanol (meth)acrylate; and

[0205] (Meth)acrylates containing alkoxy modifications such as EO and PO (e.g., having 1-10, such as 2, 4, 6, 6 or 8, preferably 1-5 EO and / or PO units), for example, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate.

[0206] As the (meth)acryloyl groups, acryloylmorpholine and the like, 2-methacryloylethoxysuccinate, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dipropylacrylamide and the like can be mentioned.

[0207] As styrene compounds there may be mentioned chloromethylstyrene and α-methylstyrene.

[0208] As the acid anhydrides containing ethylenically unsaturated double bonds, maleic anhydride and the like can be mentioned.

[0209] Mention may be made, as ethylene derivatives, of vinyl esters, preferably of C2-C6 monocarboxylic acids, for example vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate or mixtures thereof.

[0210] The free radical polymerizable monofunctional compound in monomeric form can be 10-85 wt % (e.g., 15 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt %, 70 wt %, 80 wt % or 82 wt %), preferably 20-82 wt %, 30-82 wt %, 40-80 wt %, or 50-80 wt %, based on the total weight of the photocurable composition of the present invention.

[0211] Free radical polymerizable compound (monomer) having two or more functional groups

[0212] The reaction activity of the free radical polymerizable compound of the 2-functional group is higher than that of the monofunctional compound, and the surface curability of the ink can be improved. Its viscosity is lower than that of the free radical polymerizable trifunctional compound, and by using it in combination with the monofunctional compound, it can be used as a diluent for trifunctional and more functional compounds, so that the viscosity of the photocurable composition and the photosensitive ink of the present invention is reduced and the reactivity is improved.

[0213] As bifunctional free-radically polymerizable compounds, mention may be made, for example, of di(meth)acrylates of diols or triols having 2 to 12, such as 2, 4, 6, 8 or 10, carbon atoms, di(meth)acrylates of polyethylene glycol or polypropylene glycol having a number average molecular weight of not more than 1500, such as not more than 1200, wherein these compounds are optionally modified with EO or PO, such as with 5 to 15 EO and / or PO; as specific examples, mention may be made of 2-hydroxy-3-acryloxypropyl(meth)acrylate, neopentyl glycol di(meth)acrylate, Acrylates, 1,3-butanediol di(meth)acrylate, 2-methyl-1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, ethoxylated 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate acrylate, polyethylene glycol #400 di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol #400 di(meth)acrylate, polypropylene glycol #700 di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate, polyethylene glycol #600 di(meth)acrylate ) acrylate, polyethylene glycol #1000 di(meth)acrylate, ethoxylated polypropylene glycol #700 di(meth)acrylate, polypropylene glycol #400 di(meth)acrylate, bisphenol A di(meth)acrylate (may contain different alkoxy segments such as EO and PO), hydrogenated bisphenol A di(meth)acrylate (may contain different alkoxy segments such as EO and PO), dicyclopentadiene, 2,2-bis(4-(methacryloyloxypolyethoxy)phenyl)propane (the average number of EO units is 5-15 per molecule), etc. One or more of them can be used.

[0214] Preferred are polyethylene glycol di(meth)acrylates having a number average molecular weight of not more than 1200 (eg, not more than 800) and 2,2-bis(4-(methacryloyloxypolyethoxy)phenyl)propane (the average number of EO units is 5 to 15 per molecule) and mixtures thereof.

[0215] The difunctional free radical polymerizable compound can be 0-80 wt % or 10-80 wt %, for example 5 wt %, 20 wt %, 30 wt %, 40 wt %, 50 wt %, 60 wt % or 70 wt %, based on the total weight of the photocurable composition of the present invention.

[0216] Free radical polymerizable compound (monomer) having three or more functional groups

[0217] As free radical polymerizable compounds having three or more functional groups, compounds having three or more (meth)acrylate groups can be mentioned. Specific examples include: trimethylolpropane triacrylate, trimethylolmethane triacrylate, ethylene oxide-modified trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane triacrylate, epichlorohydrin-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetra(meth)acrylate, tetramethylolmethane tetraacrylate, ethylene oxide-modified phosphoric acid triacrylate, propylene oxide-modified phosphoric acid triacrylate, epichlorohydrin-modified glycerol triacrylate, dipentaerythritol hexaacrylate, di(trimethylol)propane tetraacrylate, or multifunctional acrylates represented by silsesquioxane-modified products thereof, or methacrylate monomers corresponding thereto, ε-caprolactone-modified triacryloyloxyethyl isocyanurate, and the like.

[0218] The amount of the radically polymerizable compound having three or more functional groups may be 0-80 wt % or 5-80 wt %, for example 10, 20, 30, 40, 50, 60 or 70 wt %, based on the total weight of the photocurable composition of the present invention.

[0219] Free radical polymerizable resin

[0220] In one embodiment of the present invention, the free radical photopolymerizable compound comprises a free radical polymerizable compound in the form of a resin (including an oligomer or a prepolymer), also referred to as a free radical polymerizable resin. As free radical polymerizable resins, mention may be made of epoxy (meth) acrylate resins, polyester (meth) acrylates, polyurethane (meth) acrylates, ethylenically unsaturated polyesters, amino (meth) acrylate resins, photoimageable alkali-soluble resins, and the like. According to the present invention, it is advantageous to use epoxy (meth) acrylate resins, polyester (meth) acrylates, polyurethane (meth) acrylates, or combinations thereof.

[0221] The epoxy (meth) acrylate resin is preferably bisphenol A epoxy (meth) acrylate, bisphenol A epoxy acrylate diluted with tripropylene glycol di(meth) acrylate or a combination thereof, such as bisphenol A epoxy acrylate WSR-U125 from Wuxi Resin Factory, bisphenol A epoxy acrylate 621A-80 diluted with 20% tripropylene glycol diacrylate from Changxing Chemical Company of China Taiwan, modified bisphenol A epoxy acrylate 623-100 from Changxing Chemical Company of China Taiwan, modified bisphenol A epoxy acrylate 6231A-80 diluted with 20% tripropylene glycol diacrylate from Changxing Chemical Company of China Taiwan.

[0222] The polyester (meth)acrylate is preferably a hyperbranched polyester acrylic resin with high functionality, especially a hyperbranched polyester acrylic resin with a functionality of 5-30, such as a hyperbranched polyester acrylic prepolymer with a functionality of 6-20. For example, hyperbranched polyester acrylic prepolymer 932-100 (6 functionality) from Wuxi Knox Company, hyperbranched polyester acrylic prepolymer CN2300 (8 functionality), CN2301 (9 functionality), CN2302 (16 functionality) from Sartomer Company, USA, etc. The polyester (meth)acrylate can also be polyester polyol acrylic resin diluted with 20% ethoxylated trimethylolpropane triacrylate.

[0223] The polyurethane (meth) acrylate may be an aliphatic polyurethane (meth) acrylate resin and / or an aromatic polyurethane (meth) acrylate resin. For this purpose, mention may be made of aliphatic polyurethane hexaacrylate 6145-100, 6161-100, aliphatic polyurethane diacrylate 611B-85 diluted with 15% 1,6-hexanediol diacrylate (HDDA), and aliphatic polyurethane diacrylate 6141H-80 from Changxing Chemical Co., Ltd., Taiwan, China; aliphatic polyurethane acrylate CN9013 (9 functionalities) from Sartomer Co., Ltd., USA; aliphatic polyurethane acrylate CN966B85 (2 functionalities) diluted with 15% 1,6-hexanediol diacrylate (HDDA) from Sartomer Co., Ltd., USA; aliphatic polyurethane acrylate CN962 (2 functionalities) from Allnex Resins (China) Co., Ltd. 220, aromatic polyurethane acrylate (6 functionalities); Guangzhou Runao Chemical Materials Co., Ltd. 8091, difunctional polyurethane acrylate.

[0224] The functionality of the free radical polymerizable resin may be 2-20 (eg, 3, 4, 5, 6, 8, 10, 12, 15, 18), preferably 2-12 or 2-8.

[0225] The number average molecular weight of the free radical polymerizable resin may be 600-5000 g / mol (eg, 700, 800, 900, 1000, 1200, 1500, 2000, 3000, 4000 or 4500 g / mol), preferably 800-4000 g / mol.

[0226] In one embodiment, the free radical photopolymerizable compound comprises a free radical polymerizable resin and a monofunctional free radical polymerizable monomer, preferably the free radical polymerizable resin is polyurethane (meth)acrylate, and the monofunctional free radical polymerizable monomer is a (meth)acryloyl group, such as acryloyl morpholine.

[0227] Component (d): electron-donating reducing agent

[0228] The photocurable composition of the present invention comprises at least one electron donating reducing agent (d). In one embodiment, the electron donating reducing agent is selected from sulfinic acid and its salts, salts of ferrocyanide, ascorbic acid and its salts, phenylglycine compounds and aryl borate, preferably phenylglycine compounds and aryl borate, such as tetraphenylborate and N-phenylglycine.

[0229] In one embodiment, the weight ratio of the electron donating reducing agent to the photopolymerization initiator is 5:1-1:50 (e.g., 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:48), preferably 1:1-1:40, and more preferably 1:2-1:20.

[0230] In one embodiment, the amount of the electron donating reducing agent is 0.05-2.5 wt % (e.g., 0.06 wt %, 0.07 wt %, 0.08 wt %, 0.09 wt %, 0.1 wt %, 0.2 wt %, 0.5 wt %, 0.8 wt %, 1 wt %, 1.2 wt %, 1.5 wt %, 1.8 wt %, 2 wt % or 2.2 wt %), preferably 0.08-1.2 wt %, based on the total weight of the photocurable composition.

[0231] Component (e): Aryl phosphorus compound

[0232] The aryl phosphorus compound is especially an aryl phosphorus compound having a trivalent phosphorus atom, for example, selected from phosphine compounds having 1 to 3 phenyl rings, such as triphenylphosphine, and phosphites having 1 to 3 phenyl rings. In a preferred embodiment, the aryl phosphorus compound is selected from triphenylphosphine, triphenylphosphite, tris(nonylphenyl)phosphite, tritolylphosphite, phenyl mono(2-ethylhexyl)phosphite, diphenyl monodecylphosphite, diphenyl mono(tridecyl)phosphite, tetraphenyldipropylene glycol diphosphite, tetra(C 12 -C 15 diphenyl phosphite, 4,4'-butylenebis(3-methyl-6-tert-butylphenyltricosylphosphite), tris(2,4-di-tert-butylphenyl)phosphite and isodecyl diphenyl phosphite.

[0233] In a preferred embodiment, the aryl phosphorus compound is triphenylphosphine.

[0234] In one embodiment, the weight ratio of the aryl phosphorus compound to the photopolymerization initiator is 5:1-1:50 (e.g., 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40 or 1:45), preferably 1:1-1:40, and more preferably 1:2-1:20.

[0235] In one embodiment, the weight ratio of the electron donating reductant to the aryl phosphorus compound is 10:1-1:10 (9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8 or 1:9), preferably 5:1-1:5, more preferably 3:1-1:3.

[0236] In one embodiment, the amount of the aryl phosphorus compound is 0.05-2.5 wt % (e.g., 0.06 wt %, 0.07 wt %, 0.08 wt %, 0.09 wt %, 0.1 wt %, 0.12 wt %, 0.15 wt %, 0.18 wt %, 0.2 wt %, 0.25 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1 wt %, 1.2 wt %, 1.5 wt %, 1.8 wt %, 2 wt % or 2.2 wt %), preferably 0.08-2 wt % or 0.08-1.2 wt %, based on the total weight of the photocurable composition.

[0237] Colorants

[0238] In one embodiment, the photocurable composition comprises at least one colorant, such as white, blue, green, purple, yellow, red and black colorants, etc. These colorants may be pigments or dyes.

[0239] If a pigment is used, the particle size of the pigment may be 1-200 nm (e.g., 2, 4, 5, 8, 10, 20, 40, 50, 80, 100, 120, 150 or 180 nm, preferably 1-150 nm or 1-100 nm or 1-50 nm.

[0240] The coloring agents may be used alone or in mixture of two or more.

[0241] As the white pigment, there may be mentioned white pigments such as titanium oxide, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, hollow resin particles, zinc sulfide and the like.

[0242] As black colorants, carbon, aniline black, iron oxide, etc. can be mentioned. As blue colorants, phthalocyanine blue, etc. can be mentioned. As green colorants, phthalocyanine green, iodine green, etc. can be mentioned. As purple colorants, crystal violet can be mentioned. As yellow dyes, disazo yellow can be mentioned. In addition, rhodamine B can also be mentioned.

[0243] The amount of the colorant is 0.05-20 wt % (e.g., 0.06 wt %, 0.07 wt %, 0.08 wt %, 0.09 wt %, 1 wt %, 1.2 wt %, 1.5 wt %, 1.8 wt %, 2 wt %, 2.5 wt % or 3 wt %), preferably 0.08-10 wt % or 0.08-5 wt % or 0.1-2 wt % based on the total weight of the photocurable composition.

[0244] Solvents

[0245] The photocurable composition of the present invention may also optionally include an organic solvent. The selection of organic solvent is conventional. As an organic solvent, aromatic hydrocarbons such as benzene and toluene may be mentioned, halogenated alkanes such as chloroform, methylene chloride, ethyl chloride, ketones such as acetone, butanone, amyl ketone, etc., alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, and glycol ethers, glycol ether acetates, propylene glycol ethers, propylene glycol ether acetates, etc. The amount of solvent may be 0-20% by weight (such as 1% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight or 18% by weight), or 0-15% by weight, or 0-10% by weight, or 0-5% by weight. In one embodiment, the photocurable composition of the present invention may also be solvent-free.

[0246] In one embodiment, the photocurable composition of the present invention comprises:

[0247] (a) 0.001-5 wt % of at least one polymethine anthocyanin compound as an infrared absorbing photosensitizer;

[0248] (b) 0.1 to 10 wt % of at least one photopolymerization initiator;

[0249] (c) 60 to 98.5% by weight of at least one photopolymerizable compound;

[0250] (d) 0.05-2.5 wt % of at least one electron donating reducing agent;

[0251] (e) 0.05 to 2.5 weight percent of at least one aryl phosphorus compound; and

[0252] 0-20 wt % solvent;

[0253] In each case based on the total weight of the photocurable composition.

[0254] In one embodiment, the photocurable composition of the present invention comprises:

[0255] (a) 0.001-5 wt % of at least one polymethine anthocyanin compound as an infrared absorbing photosensitizer;

[0256] (b) 0.1 to 10 wt % of at least one photopolymerization initiator;

[0257] (c) 70-98.5 wt % of at least one photopolymerizable compound and the light;

[0258] (d) 0.05-2 wt % of at least one electron donating reducing agent;

[0259] (e) 0.05 to 2% by weight of at least one aryl phosphorus compound, and

[0260] 0-20 wt % solvent;

[0261] In each case based on the total weight of the photocurable composition.

[0262] In one embodiment, the photocurable composition of the present invention comprises:

[0263] (a) 0.001-5 wt % of at least one polymethine anthocyanin compound as an infrared absorbing photosensitizer;

[0264] (b) 0.1 to 10 wt % of at least one photopolymerization initiator;

[0265] (c) 80 to 98.5 wt % of at least one photopolymerizable compound;

[0266] (d) 0.05-2.5 wt. % of at least one electron donating reducing agent; and

[0267] (e) 0.05 to 2.5% by weight of at least one aryl phosphorus compound;

[0268] In each case based on the total weight of the photocurable composition.

[0269] In one embodiment, the photocurable composition of the present invention comprises:

[0270] (a) 0.001-0.5 wt % of at least one polymethine anthocyanin compound as an infrared absorbing photosensitizer;

[0271] (b) 0.1 to 10 wt % of at least one photopolymerization initiator;

[0272] (c) 85 to 98.5 weight percent of at least one photopolymerizable compound;

[0273] (d) 0.05-2.5 wt. % of at least one electron donating reducing agent; and

[0274] (e) 0.05 to 2.5% by weight of at least one aryl phosphorus compound;

[0275] In each case based on the total weight of the photocurable composition.

[0276] Uses and products

[0277] One aspect of the present invention relates to the use of the photocurable composition of the present invention in 3D printing, especially SLA 3D printing, wherein the photocurable composition is preferably processed using a NIR (laser) light source with an emission wavelength of 700-2000nm, preferably 750-900nm.

[0278] One aspect of the present invention relates to a photocurable article obtained from the photocurable composition of the present invention. The photocurable article can be obtained by 3D printing, especially SLA 3D printing, wherein the photocurable composition is preferably processed using a NIR (laser) light source with an emission wavelength of 700-2000nm, preferably 750-900nm.

[0279] Example

[0280] The present invention is specifically described with reference to the following examples, but the present invention is not limited to these examples. It should be noted that, unless otherwise specified, parts refer to parts by weight, amounts refer to weight, and percentages refer to percentages by weight.

[0281] raw material:

[0282] ACMO: 4-acryloylmorpholine;

[0283] 220: aromatic polyurethane acrylate; number average molecular weight (Mn) of 1000 g / mol, functionality of 6, purchased from Allnex Resins (China) Co., Ltd.;

[0284] LuCure8091: difunctional polyurethane acrylate, purchased from Guangzhou Runao Chemical Materials Co., Ltd.;

[0285] Carbon black: particle size 30 nm, purchased from Beijing Inokai Technology Co., Ltd.

[0286] Rhodamine B dye: purchased from Beijing Inokai Technology Co., Ltd.

[0287] method

[0288] 1. The test method for the curing rate of the composition is as follows:

[0289] The Fourier transform infrared spectroscopy (FTIR) analysis technique was used to measure the characteristic peaks of acrylate double bonds (ACMO using 820-773cm -1 Or other monomers or oligomers use 1660-1600cm -1 ) t And the absorbance A0 at its characteristic peak before the sample is exposed. Then the curing rate of the photopolymerization reaction of each component is calculated according to the following formula:

[0290] Curing rate = ((A0-A t ) / A0)×100%

[0291] When several polymerizable compounds are contained, the curing rate is an average value of the curing rates of the several polymerizable compounds.

[0292] 2. The test method for the thermal stability of the composition is as follows:

[0293] The crucible containing the photocurable composition for 3D printing was heated from 25°C to 10°C min using a Mettler differential scanning calorimeter (DSC 1). -1 The temperature was raised to 250°C at a rate of 1.5°C, and the heating process was carried out in a nitrogen environment. After the test, a curve of temperature relative to heat flow rate was obtained, and the starting value of the first exothermic peak was determined as the thermal decomposition temperature of the 3D printing photocurable composition.

[0294] 3. The composition was tested for 3D printing as follows:

[0295] The photocurable composition was placed in a liquid reservoir, and a near-infrared light-curing SLA 3D printer (Wuhan Duyi Technology Co., Ltd.) was debugged to set an appropriate laser intensity (about 125 mW cm-2 ) and scanning speed (about 200 mm s -1 After processing, the support structure was removed by cleaning with a solvent and an 820nm LED light source (with a light intensity of 1.5W cm -2 ) is post-cured to obtain a printed product.

[0296] 4. The test methods for the light absorption and light degradation properties of the composition are as follows:

[0297] The photocurable composition was placed in a quartz sheet interlayer (quartz sheet was 45 mm long, 12 mm wide, and 1 mm thick), and the thickness of the interlayer was about 30 microns. The absorption value of the interlayer in the range of 400-900 nm was measured using a Shimadzu UV-3600 UV-vis-NIR spectrophotometer to obtain the light absorption curve of the 3D printed photocurable composition. The interlayer was then irradiated with an 820 nm LED light source, and the absorption curve of the interlayer under different irradiation times was tested to obtain the photodegradation properties of the photocurable composition.

[0298] 5. The mechanical properties test method of the printed product is as follows:

[0299] The stress-strain curve of the printed tensile rod was tested using an Instron electronic mechanical universal testing machine (Instron 5969) at a tensile speed of 15 mm / min. Three tensile rods of the same size printed simultaneously were tested to obtain the mechanical properties of the printed product.

[0300] Example 1 - Absorption properties of photocurable compositions in the near infrared region

[0301] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition, and the specific formula is shown in Table 1. The absorption value of the interlayer in the range of 400-900nm is measured by Shimadzu UV-3600 UV-vis-NIR spectrophotometer.

[0302] Table 1: Photocurable composition formulation

[0303]

[0304] The light absorption curve test results of the photocurable composition prepared in Example 1 are as follows: Figure 1 The 3D printing photocurable composition has excellent light absorption properties in the NIR light region, and its maximum absorption wavelength is around 800nm, which has good compatibility with the 808nm laser light source configured for near-infrared SLA 3D printing.

[0305] Example 2 - Absorption properties of photocurable compositions in the near infrared region

[0306] Compared with the composition of Example 1, the composition of Example 2 adds infrared absorption photosensitizer S44, uses iodonium salt IS41 as an initiator, and changes the mass ratio of the components.

[0307] S132 and S44 were selected as infrared absorption photosensitizers, iodonium salt IS41 was used as initiator, and acryloylmorpholine ACMO was used as monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition, and the specific formula is shown in Table 2. The absorption value of the interlayer in the range of 400-900nm is measured by Shimadzu UV-3600 UV-vis-NIR spectrophotometer.

[0308] Table 2: Photocurable composition formulation

[0309]

[0310] The light absorption curve test results of the photocurable composition prepared in Example 2 are as follows: Figure 2 The 3D printing photocurable composition has excellent light absorption properties in the NIR light region, and its maximum absorption wavelength is around 800nm, which has good compatibility with the 808nm laser light source configured for near-infrared SLA 3D printing.

[0311] Example 3-Polymerization curing rate and polymerization rate of photocurable composition under near-infrared light source irradiation

[0312] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was used as the initiator, and acryloylmorpholine ACMO was used as the monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition, and the specific formula is shown in Table 3. Exposure is performed according to the exposure conditions in Table 4, and then the curing rate is tested by Fourier transform infrared spectroscopy (FTIR).

[0313] Table 3: Photocurable composition formulation

[0314]

[0315] Table 4: Exposure conditions

[0316] light source Light intensity Exposure time Substrate Coating thickness 808 Laser <![CDATA[825mW cm -2 ]]> 50s Potassium Bromide Tablets 30μm

[0317] The test results of the photopolymerization kinetics of the photocurable composition prepared in Example 3 are as follows: Figure 3-4The 3D printing photocurable composition, under the irradiation of NIR laser light source with an emission wavelength of 808nm, can achieve a curing rate of about 80% for monomers and oligomers, and a peak polymerization rate of 40%s -1 , a higher curing rate and a faster polymerization rate can be achieved simultaneously, indicating that the composition has a basis for preparing polymer materials through 3D printing processing.

[0318] Example 4 - Polymerization curing rate and polymerization rate of a photocurable composition containing carbon black under near-infrared light source irradiation

[0319] Compared with the composition of Example 3, the composition of Example 4 additionally contains carbon black as a pigment additive.

[0320] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, triphenylphosphine is an aromatic phosphorus compound, and carbon black is a pigment additive to prepare a photocurable composition, and the specific formula is shown in Table 5. Exposure is performed according to the exposure conditions in Table 6, and then the curing rate is tested by Fourier transform infrared spectroscopy (FTIR).

[0321] Table 5: Photocurable composition formulation

[0322]

[0323] Table 6: Exposure conditions

[0324] light source Light intensity Exposure time Substrate Coating thickness 808 Laser <![CDATA[825mW cm -2 ]]> 50s Potassium Bromide Tablets 30μm

[0325] The test results of the photopolymerization kinetics of the photocurable composition prepared in Example 4 are as follows: Figure 5-6 The 3D printing photocurable composition containing carbon black, under the irradiation of NIR laser light source with an emission wavelength of 808nm, can achieve a curing rate of about 80% for monomers and oligomers, and a peak polymerization rate of 27%s -1 , a higher curing rate and a faster polymerization rate can be achieved simultaneously. The addition of carbon black reduces the polymerization rate to a certain extent, but it still meets the printing requirements, indicating that the composition has a basis for preparing polymer materials through 3D printing processing, and has the potential to prepare colored materials through NIR SLA 3D printing.

[0326] Example 5-Polymerization curing rate and polymerization rate of photocurable composition under near-infrared light source irradiation

[0327] Compared with the composition of Example 3, the composition of Example 5 adds infrared absorption photosensitizer S44, uses iodonium salt IS41 as an initiator, and changes the mass ratio of the components.

[0328] S132 and S44 were selected as infrared absorption photosensitizers, iodonium salt IS41 was used as initiator, and acryloylmorpholine ACMO was used as monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition, and the specific formula is shown in Table 7. Exposure is performed according to the exposure conditions in Table 8, and then the curing rate is tested by Fourier transform infrared spectroscopy (FTIR).

[0329] Table 7: Photocurable composition formulation

[0330]

[0331]

[0332] Table 8: Exposure conditions

[0333] light source Light intensity Exposure time Substrate Coating thickness 808 Laser <![CDATA[825mW cm -2 ]]> 50s Potassium Bromide Tablets 30μm

[0334] The test results of the photopolymerization kinetics of the photocurable composition prepared in Example 5 are as follows: Figure 7-8 The 3D printing photocurable composition, under the irradiation of NIR laser light source with an emission wavelength of 808nm, can achieve a curing rate of about 80% for monomers and oligomers, and a peak polymerization rate of 27%s -1 , a higher curing rate and a faster polymerization rate can be achieved simultaneously, indicating that the composition has a basis for preparing polymer materials through 3D printing processing.

[0335] Example 6-Polymerization curing rate and polymerization rate of a photocurable composition containing a pigment under near-infrared light source irradiation

[0336] Compared with the composition of Example 5, the composition of Example 6 additionally contains Rhodamine B as a pigment additive.

[0337] S132 and S44 were selected as infrared absorption photosensitizers, IS41 as initiator, and acryloylmorpholine ACMO as monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, triphenylphosphine is an aromatic phosphorus compound, and rhodamine B is a pigment additive to prepare a photocurable composition, and the specific formula is shown in Table 9. Exposure is performed according to the exposure conditions in Table 10, and then the curing rate is tested by Fourier transform infrared spectroscopy (FTIR).

[0338] Table 9: Photocurable composition formulation

[0339]

[0340] Table 10: Exposure conditions

[0341] light source Light intensity Exposure time Substrate Coating thickness 808 Laser <![CDATA[825mW cm -2 ]]> 50s Potassium Bromide Tablets 30μm

[0342] The test results of the photopolymerization kinetics of the photocurable composition prepared in Example 6 are as follows: Figure 9-10 The 3D printing photocurable composition, under the irradiation of NIR laser light source with an emission wavelength of 808nm, can achieve a curing rate of about 78% for monomers and oligomers, and a peak polymerization rate of 23%s -1 , a higher curing rate and a faster polymerization rate can be achieved simultaneously. The addition of rhodamine B reduces the polymerization rate to a certain extent, but it still meets the printing requirements, indicating that the composition has a basis for preparing polymer materials through 3D printing processing, and has the potential to prepare colored materials through NIR SLA 3D printing.

[0343] Example 7 - Thermal stability of photocurable compositions

[0344] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure 8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition, and the specific formula is shown in Table 11. The thermal stability of the composition was tested using a Mettler differential scanning calorimeter (DSC 1).

[0345] Table 11: Photocurable composition formulation

[0346]

[0347] The test results of the temperature of the photocurable composition prepared in Example 7 relative to the heat flow rate are as follows: Fig.11 The 3D printing photocurable composition has good thermal stability, and the initial thermal reaction temperature is about 100°C, which can meet the actual printing needs and ensure the accuracy and safety in the 3D printing process.

[0348] Example 8 - Thermal stability of photocurable compositions

[0349] Compared with the composition of Example 7, the composition of Example 8 adds infrared absorption photosensitizer S44, uses iodonium salt IS41 as an initiator, and changes the mass ratio of the components.

[0350] Select S132 as infrared absorption photosensitizer, S44 as infrared absorption photosensitizer, iodonium salt IS41 as initiator, acryloyl morpholine ACMO as monomer, 220 and LuCure 8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition, and the specific formula is shown in Table 12. The thermal stability of the composition is tested using a Mettler differential scanning calorimeter (DSC 1).

[0351] Table 12: Photocurable composition formulation

[0352]

[0353] The test results of the temperature of the photocurable composition prepared in Example 8 relative to the heat flow rate are as follows: Fig.12 The 3D printing photocurable composition has good thermal stability, and the initial thermal reaction temperature is about 100°C, which can meet the actual printing needs and ensure the accuracy and safety in the 3D printing process.

[0354] Example 9 - Manufacturing 3D printed products by SLA 3D printing

[0355] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition. The specific formula is shown in Table 13. Then, according to the printing parameters in Table 14, a near-infrared light-curing SLA 3D printer is used to prepare the product. Then, an 820nm LED light source is used for post-curing (light intensity is 1.5W cm -2 ) for 30 minutes.

[0356] Table 13: Photocurable composition formulation

[0357]

[0358] Table 14: Printing parameters

[0359]

[0360] The printed product of the photocurable composition of Example 9 is shown in FIG. 13( a ), indicating that the composition has the ability to prepare polymer materials through 3D printing processing.

[0361] Example 10 - Manufacturing colored 3D printed products by SLA 3D printing

[0362] Compared with the photocurable composition of Example 9, carbon black is newly added as a pigment additive in the photocurable composition of Example 10.

[0363] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 as oligomers, sodium tetraphenylborate as a reducing agent, triphenylphosphine as an aromatic phosphorus compound, and carbon black as a pigment additive were used to prepare a photocurable composition. The specific formula is shown in Table 15. Then, according to the printing parameters in Table 16, a near-infrared light-curing SLA 3D printer was used to prepare the material. Then, an 820nm LED light source was used for post-curing (the light intensity was 1.5W cm -2 ) for 30 minutes.

[0364] Table 15: Photocurable composition formulation

[0365]

[0366] Table 16: Exposure conditions

[0367]

[0368]

[0369] Example 10 Printing products of the photocurable composition such as Fig.14 As shown, it is shown that the composition has the ability to prepare polymer materials through 3D printing. In addition, the addition of carbon black can color the product, thereby successfully manufacturing a black product.

[0370] Example 11 - Manufacturing 3D printed products by SLA 3D printing

[0371] Compared with Example 9, the photocurable composition of Example 11 adds infrared absorption photosensitizer S44, uses iodonium salt IS41 as an initiator, and changes the mass ratio of the components.

[0372] S132 and S44 were selected as infrared absorption photosensitizers, iodonium salt IS41 was used as initiator, and acryloylmorpholine ACMO was used as monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition. The specific formula is shown in Table 17. Then, according to the printing parameters in Table 18, a near-infrared light-curing SLA 3D printer is used to print the product. Then, an 820nm LED light source is used for post-curing (light intensity is 1.5W cm -2 ) for 30 minutes.

[0373] Table 17: Photocurable composition formulation

[0374]

[0375] Table 18: Exposure conditions

[0376]

[0377] The 3D printed product of the photocurable composition of Example 11 is as follows Fig.15 As shown, it is shown that the composition has the ability to prepare polymer materials through 3D printing processing.

[0378] Example 12 - Manufacturing colored 3D printed products by SLA 3D printing

[0379] Compared with the photocurable composition of Example 11, the photocurable composition of Example 12 additionally contains Rhodamine B as a pigment additive.

[0380] S132 and S44 were selected as infrared absorption photosensitizers, iodonium salt IS41 was used as initiator, and acryloylmorpholine ACMO was used as monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, triphenylphosphine is an aromatic phosphorus compound, and rhodamine B is a pigment additive to prepare a light-curable composition. The specific formula is shown in Table 19. Then, according to the printing parameters in Table 20, a near-infrared light-curing SLA 3D printer is used to print the product. Then, an 820nm LED light source is used for post-curing (light intensity is 1.5Wcm -2 ) for 30 minutes.

[0381] Table 19: Photocurable composition formulation

[0382]

[0383] Table 20: Exposure conditions

[0384]

[0385] The printed product of the photocurable composition of Example 12 is as follows Fig.16 As shown, it is shown that the composition has the ability to prepare polymer materials through 3D printing. In addition, the addition of rhodamine B can color the product and successfully manufacture a red product.

[0386] Comparative Example 1 - SLA 3D printing comparison without reducing agent

[0387] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, triphenylphosphine is an aromatic phosphorus compound, and a photocurable composition is prepared. The specific formula is shown in Table 21. Compared with Example 9, this example does not add a reducing agent, sodium tetraphenylborate. Then, according to the printing parameters in Table 22, a near-infrared light-curing SLA 3D printer is used to prepare the product.

[0388] Table 21: Photocurable composition formulation

[0389]

[0390] Table 22: Printing parameters

[0391]

[0392] Compared with Example 9, the photocurable composition of Comparative Example 1 cannot successfully print a molded product, indicating that the electron-donating reducing agent plays a very significant role in the photocurable composition for 3D printing and is indispensable. Comparative Example 2 - SLA 3D printing comparison without the presence of an aromatic phosphine compound

[0393] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, and the reducing agent is sodium tetraphenylborate, and a photocurable composition is prepared. The specific formula is shown in Table 23. Compared with Example 9, this example does not add an aryl phosphine compound. Then, according to the printing parameters in Table 24, a near-infrared light-curing SLA 3D printer is used to prepare the product.

[0394] Table 23: Photocurable composition formulation

[0395]

[0396] Table 24: Printing parameters

[0397]

[0398] Compared with Example 9, the photocurable composition of Comparative Example 2 cannot successfully print a molded product, indicating that the role of the aryl phosphine compound in the 3D printing photocurable composition is very obvious and indispensable. Comparative Example 3 - Comparison of SLA 3D printing without a reducing agent and with an aryl phosphine compound

[0399] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, and a photocurable composition is prepared. The specific formula is shown in Table 25. Compared with Example 9, this example does not add a reducing agent and an aryl phosphine compound. Then, according to the printing parameters in Table 26, a near-infrared light-curing SLA 3D printer is used to prepare the product.

[0400] Table 25: Photocurable composition formulation

[0401]

[0402] Table 26: Printing parameters

[0403]

[0404]

[0405] Compared with Example 9, the photocurable composition of Comparative Example 3 cannot successfully print out a molded product, which shows that the electron-donating reducing agent and the aromatic phosphine compound play a very obvious role in the 3D printing photocurable composition and are both indispensable.

[0406] Example 13 - Photolysis reaction under NIR light source irradiation

[0407] This example is used to illustrate that the photoinitiator system in the 3D printing photocurable composition of the present invention can undergo a photolysis reaction.

[0408] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 were used as oligomers, sodium tetraphenylborate was used as a reducing agent, and triphenylphosphine was used as an aromatic phosphorus compound to prepare a photocurable composition. The specific formula is shown in Table 27. An 820 nm LED light source (light intensity 825 mW cm -2 ) irradiate the composition in the interlayer for different irradiation times, and then use a Shimadzu UV-3600 UV-vis-NIR spectrophotometer to measure the absorbance of the interlayer in the range of 400-900 nm.

[0409] Table 27: Photocurable composition formulation

[0410]

[0411] The photolysis curve of the photocurable composition of Example 13 is as follows: Fig.17 As shown, the absorption value of the photocurable composition decreases rapidly with time, indicating that the photoinitiator system in the composition can undergo photolysis reaction under the irradiation of near-infrared light source.

[0412] Example 14 - Photolysis reaction under NIR light source irradiation

[0413] Compared with the photocurable composition of Example 13, the photocurable composition of Example 14 contains an infrared absorption photosensitizer S44, uses an iodonium salt IS41 as an initiator, and changes the mass ratio of the components.

[0414] S132 and S44 were selected as infrared absorption photosensitizers, iodonium salt IS41 was used as initiator, and acryloylmorpholine ACMO was used as monomer. 220 and LuCure8091 were used as oligomers, sodium tetraphenylborate was used as a reducing agent, and triphenylphosphine was used as an aromatic phosphorus compound to prepare a photocurable composition. The specific formula is shown in Table 28. An 820 nm LED light source (light intensity 825 mW cm -2 ) irradiate the composition in the interlayer for different irradiation times, and then use a Shimadzu UV-3600 UV-vis-NIR spectrophotometer to measure the absorbance of the interlayer in the range of 400-900 nm.

[0415] Table 28: Photocurable composition formulation

[0416]

[0417]

[0418] The photolysis curve of the photocurable composition of Example 14 is as follows Fig.18 As shown, the absorption value of the photocurable composition decreases rapidly with time, indicating that the photoinitiator system in the composition can undergo photolysis reaction under the irradiation of near-infrared light source.

[0419] Example 15 - Mechanical properties testing of products manufactured by SLA 3D printing

[0420] This example is used to illustrate that the product prepared by the 3D printing photocurable composition of the present invention has good mechanical properties.

[0421] S132 was selected as the infrared absorption photosensitizer, iodonium salt IS1 was selected as the initiator, and acryloylmorpholine ACMO was selected as the monomer. 220 and LuCure8091 are oligomers, sodium tetraphenylborate is a reducing agent, and triphenylphosphine is an aromatic phosphorus compound to prepare a photocurable composition (its formula is the same as that of Example 9), and the specific formula is shown in Table 29. According to the printing parameters of Table 30, a near-infrared light-curing SLA 3D printer is used to prepare a stretch rod. The overall length of the stretch rod is 55 mm, the overall width is 10.7 mm, the overall thickness is 2.5 mm, and the width at the break is 2.8 mm. Then, an 820 nm LED light source is used for post-curing (the light intensity is 1.5 W cm -2), the time is 30min. Then, the stress-strain test is carried out at 25°C using an electronic mechanical universal testing machine (Instron 5969), and the stretching rate is set to 15mm / min.

[0422] Table 29: Photocurable composition formulation

[0423]

[0424] Table 30: Exposure conditions

[0425]

[0426] The tensile rod prepared in Example 15 is shown in FIG. 13( b ), and three tensile rods with the same size are printed at the same time. The stress-strain curve of the tensile rod is shown in FIG. Fig.19 The values ​​of tensile stress and tensile strain are shown in Table 31. The results show that the tensile rod prepared by SLA 3D printing has good mechanical properties, and the data between the three samples are not much different, and the slopes are very close, indicating that SLA 3D printing has good printing stability.

[0427] Table 31: Tensile stress and tensile strain of tensile rods

[0428] Tensile strain (%) Tensile stress (MPa) Sample 1 1.92 41.9 Sample 2 1.94 41.7 Sample 3 2.23 48.7

Claims

1. A photocurable composition comprising the following components: (a) at least one polymethine cyanine compound as an infrared absorbing photosensitizer; (b) at least one photopolymerization initiator; (c) at least one free radical photopolymerizable compound; (d) at least one electron donating reducing agent; and (e) at least one aryl phosphorus compound.

2. The photocurable composition according to claim 1, wherein the polymethine cyanine compound as component (a) has a structure represented by formula (I): in Y + represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members and having a positive charge, Y represents a bicyclic, tricyclic or higher heterocyclic ring having 8 to 18 ring members and containing 1 or 2 nitrogen atoms as ring members, Y + The heterocyclic ring in the definition of Y may contain one or more selected from halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 branched or unbranched alkylthio or phenylthio substituents, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms; Preferred Y + / Y are the structural units shown below: Indole Salt / Indole Phenyl[e]indole salt / phenyl[e]indole and / or phenyl[c,d]indole salts / phenyl[c,d]indole, The benzene ring or naphthalene ring of the indole salt / indole, phenyl[e]indole salt / phenyl[e]indole, and phenyl[c,d]indole salt / phenyl[c,d]indole may have one or more, preferably one or two, selected from halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 branched or unbranched alkylthio or phenylthio substituents, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms; Wherein R1 is selected from C1-C 12 Branched or unbranched alkyl and C1-C 12 branched or unbranched alkoxy, Wherein the C1-C 12 Branched or unbranched alkyl and C1-C 12 Branched or unbranched alkoxy groups may be interrupted by one or more non-adjacent oxygen atoms, such as –[-CH2CHR-O-] n The polyether shown, wherein n is 1-6, and R is H or CH3; The ring carbon position indicated by the arrow is the connection site with the polymethine chain; More preferably Y + / Y are the structural units shown below: Wherein R1 is selected from C1-C 12 Branched or unbranched alkyl and C1-C 12 A branched or unbranched alkoxy group, wherein the C1-C 12 Branched or unbranched alkyl and C1-C 12 Branched or unbranched alkoxy groups may be interrupted by one or more non-adjacent oxygen atoms, such as –[-CH2CHR-O-] n The polyether shown, wherein n is 1-6, and R is H or CH3; and R2, R3 are independently selected from H, halogen, CN, nitro, C1-C 12 Branched or unbranched alkyl, C1-C 12 Branched or unbranched alkoxy, C1-C 12 A branched or unbranched alkylthio or phenylthio group, wherein the C1-C 12 Branched or unbranched alkyl, the C1-C 12 Branched or unbranched alkoxy, the C1-C 12 The alkyl groups in the branched or unbranched alkylthio group may be interrupted by one or more non-adjacent oxygen atoms; The ring carbon position indicated by the arrow is the connection site with the polymethine chain; n1, n2 are independently 0, 1 or 2; preferably 0 or 1, more preferably 1; B and C are independently selected from H, Cl-C 12 Alkyl groups may form a five-membered ring or a six-membered ring together with the carbon atoms to which they are attached; A is selected from the structures shown in A-1 to A-13: or C1-C 12 Branched or unbranched alkoxy group (A-13); in * represents the connection site with the structure of formula (I), wherein the "R2 and R2" groups are identical or different and are each independently selected from hydrogen, halogen, C1-C6 branched or unbranched alkyl, C1-C6 branched or unbranched alkoxy, C1-C6 branched or unbranched alkylthio or phenylthio, Preferably, group A is selected from the structures shown in A-1, A-2, A-4, A-5 or A-7 to A-13; When the A group is a group A-1 or A-2, n3 is 0, and when the A group is one of the groups A-3 to A-13, n3 is 1, and X - represents the counter ion.

3. The photocurable composition according to claim 2, wherein the compound of formula (I) satisfies one or more of the following conditions: R1 is selected from C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms; R2 is selected from H, halogen, nitro, C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl, the C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms; R3 is selected from H, C1-C6 branched or unbranched alkyl and C1-C6 branched or unbranched alkoxy, wherein the C1-C6 branched or unbranched alkyl and the C1-C6 branched or unbranched alkoxy may be interrupted by 1 or 2 non-adjacent oxygen atoms.

4. The photocurable composition according to claim 2 or 3, wherein B and C are independently H or form a five-membered ring or a six-membered ring together with the carbon atoms connecting them, preferably B and C form a five-membered ring or a six-membered ring together with the carbon atoms connecting them.

5. The photocurable composition according to any one of claims 2 to 4, wherein the "R2 and R2" groups are the same or different and are each independently selected from hydrogen or a C1-C6 branched or unbranched alkyl group.

6. The photocurable composition according to any one of claims 2 to 5, wherein X - Represents the following counter ions: BF4 - , [B(Ph4] - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - , Cl - Br - 、F - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - 、[C(O-SO2CF3)3] - 、[nC 12 H 25- TsO - or [NTf2] - , among which BF4 is preferred - , [B(Ph4] - PF6 - 、SbF6 - 、AsF6 - 、[PF3(C2F5)3] - 、[Al(OC(CF3)3)4] - , [B(PhF5)4] - 、[B(Ph(CF3)2)4] - 、[((CF3)2SO2)2N] - 、[((CF3)2SO2)3C] - 、[Al(Ot-C4F9)4] - 、[Al(O-(i-C3F7)CH3)4] - or [NTf2] - .

7. The photocurable composition according to any one of claims 2 to 6, wherein the polymethine cyanine compound as component (a) is selected from one or more of the following compounds S1 to S189: When n=0, it is a five-membered ring, and when n=1, it is a six-membered ring; wherein barb1 refers to the A-1 group as defined in claim 1, wherein both R2 and R2 are -CH3, and barb2 refers to the A-2 group as defined in claim 1, wherein both R2 and R2 are -CH3, Preferably, the polymethine anthocyanin compound as component (a) is selected from S132, S44 or a mixture thereof.

8. The photocurable composition according to any one of claims 1 to 7, wherein the photopolymerization initiator as component (b) is a photopolymerization initiator capable of generating free radicals in the presence of component (a).

9. The photocurable composition according to any one of claims 1 to 8, wherein the photopolymerization initiator as component (b) is selected from iodonium salt, sulfonium salt, triazine and oxime ester type photopolymerization initiators.

10. The photocurable composition according to any one of claims 1 to 9, wherein the photopolymerization initiator as component (b) is an iodonium salt, preferably selected from iodonium salts represented by formula II: in, R1'-R6' may be the same or different and are independently selected from H, halogen, nitro, C1-C 20 Branched or unbranched alkyl, C1-C 20 Branched or unbranched alkoxy and C1-C 20 Branched or unbranched alkylthio, and X' - According to claim 2 or 6, X in the compound of formula (I) - As defined, Preferably, X in the compound of formula (I) is - and X' in the compound of formula (II) - are the same.

11. The photocurable composition according to any one of claims 1 to 10, wherein the photopolymerization initiator as component (b) is selected from one or more of the following compounds IS1 to IS41: It is preferred that the photopolymerization initiator as component (b) is selected from IS1, IS41 or a mixture thereof.

12. The photocurable composition according to any one of claims 1 to 11, wherein the weight ratio of the infrared absorbing photosensitizer as component (a) to the photopolymerization initiator as component (b) is 100:1 to 1:100, preferably 1:1 to 1:100, more preferably 1:10 to 1:

100.

13. The photocurable composition according to any one of claims 1 to 12, wherein the amount of the infrared absorbing photosensitizer as component (a) is 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on the total weight of the photocurable composition.

14. The photocurable composition according to any one of claims 1 to 13, wherein the amount of the photopolymerization initiator as component (b) is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the photocurable composition.

15. A photocurable composition according to any one of claims 1 to 14, wherein the free radical photopolymerizable compound comprises at least one of a free radical polymerizable resin, a free radical polymerizable monomer having two or more functional groups, and a monofunctional free radical polymerizable monomer, preferably the free radical photopolymerizable compound comprises a free radical polymerizable resin and a free radical polymerizable monomer having two or more functional groups, or the free radical photopolymerizable compound comprises a free radical polymerizable resin and a monofunctional free radical polymerizable monomer, or the free radical photopolymerizable compound comprises a free radical polymerizable resin, a free radical polymerizable monomer having two or more functional groups, and a monofunctional free radical polymerizable monomer.

16. A photocurable composition according to any one of claims 1 to 15, wherein the electron donating reducing agent is selected from phenylglycine compounds and aryl borate salts, preferably from phenylglycine compounds and aryl borate salts, for example from sodium tetraphenylborate and N-phenylglycine.

17. The photocurable composition according to any one of claims 1 to 16, wherein the weight ratio of the electron donating reducing agent to the photopolymerization initiator is 5:1 to 1:50, preferably 1:1 to 1:40, more preferably 1:2 to 1:

20.

18. The photocurable composition according to any one of claims 1 to 17, wherein the amount of the electron donating reducing agent is 0.05 to 2% by weight, preferably 0.08 to 1.2% by weight, based on the total weight of the photocurable composition.

19. The photocurable composition according to any one of claims 1 to 18, wherein the aryl phosphorus compound is an aryl phosphorus compound having a trivalent phosphorus atom, in particular triphenylphosphine.

20. The photocurable composition according to any one of claims 1 to 19, wherein the weight ratio of the aryl phosphorus compound to the photopolymerization initiator is 5:1 to 1:50, preferably 1:1 to 1:40, more preferably 1:2 to 1:

20.

21. The photocurable composition according to any one of claims 1 to 20, wherein the weight ratio of the electron donating reducing agent to the aryl phosphorus compound is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:

3.

22. The photocurable composition according to any one of claims 1 to 21, wherein the amount of the aryl phosphorus compound is 0.05 to 2% by weight, preferably 0.08 to 1.2% by weight, based on the total weight of the photocurable composition.

23. A photocurable composition according to any one of claims 1 to 22, wherein the photocurable composition comprises at least one colorant, such as dyes and pigments, in particular the amount of the colorant is 0.05-20 wt %, preferably 0.08-10 wt % or 0.1-2 wt %, based on the total weight of the photocurable composition.

24. Use of the photocurable composition according to any one of claims 1 to 23 in 3D printing, especially SLA 3D printing, preferably using a NIR (laser) light source with an emission wavelength of 700-2000 nm, preferably 750-900 nm to process the photocurable composition.

25. A photocured product obtained from the photocurable composition according to any one of claims 1 to 23.

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