Diallyl phthalate resin-modifying compounds, methods of making and use thereof

Abstract

The present application provides a phthalic acid diallyl ester resin modifying compound, a preparation method and application thereof. The phthalic acid diallyl ester resin modifying compound has a weight average molecular weight of 5000-100000 and contains a structure shown in structural formula I, wherein 1:4≤x:y≤4:1, R1 and R2 each independently represent any one of a hydrogen atom, a C1-C20 linear or branched alkyl group, a C1-C20 alkoxy group, a C2-C20 unsaturated hydrocarbon group, a C3-C20 cyclic alkyl group, a C2-C20 ether group, a halogen atom and a halogenated hydrocarbon group. The phthalic acid diallyl ester resin modifying compound not only has solvent resistance, water resistance and scratch resistance of the phthalic acid diallyl ester resin, but also has high reactivity, and can be cured under various energy actions, especially easy to be photo-cured or heat-cured, and fast curing rate. 10 linear or branched alkyl group, a C1-C20 alkoxy group, a C 10 linear or branched alkyl group, a C1-C20 alkoxy group, C 10 unsaturated hydrocarbon group, a C3-C20 cyclic alkyl group, a C2-C 10 ether group, a halogen atom and a halogenated hydrocarbon group. The phthalic 10 acid diallyl ester resin modifying compound not only has solvent resistance, water resistance and scratch resistance of the phthalic acid diallyl ester resin, but also has high reactivity,

Description

Technical Field

[0001] This invention relates to the field of new materials technology, and more specifically, to a diallyl phthalate resin-modified compound, its preparation method, and its application. Background Technology

[0002] Oxycyclic butane compounds are widely used as reactive diluents in cationic initiation systems. Compared with free radical initiation systems, they have advantages such as small volume shrinkage, small oxygen inhibition, and strong adhesion. They are suitable for coatings, inks, and adhesives on metal and plastic surfaces, and also have broad application prospects in the field of 3D printing.

[0003] Diallyl phthalate (DAP) resin possesses excellent dielectric properties, resistance to damp heat, aging resistance, chemical corrosion resistance, and dimensional stability, making it widely used in electrical insulation materials, adhesives, and UV inks. In water-based UV ink formulations, DAP resin can improve ink emulsification during printing and adjust the degree of emulsification; it can also enhance the ink's heat resistance and reduce the impact of temperature on ink viscosity; furthermore, DAP resin can reduce the wetting and swelling problems of printing rollers caused by ink.

[0004] OSAKA SODA's patent JP5585776B2 discloses a photocurable resin composition containing an allyl polymer and diallyl phthalate resin. By introducing diallyl phthalate resin into the photocurable composition, the resulting inks, coatings, adhesives, and photoresists show significantly improved adhesion to synthetic polymer substrates, particularly plastic substrates. Dai Nippon Printing's patent JP2793611B2 discloses a method for producing simultaneously embossed decorative panels using diallyl phthalate resin. By adding diallyl phthalate resin and a photoinitiator to the ink and then performing photocuring, the solvent resistance, water resistance, and scratch resistance of the decorative panel can be improved.

[0005] However, since the allyl groups on the side chains of diallyl phthalate resin are inert groups and cannot participate in the polymerization reaction during photocuring, increasing the amount of diallyl phthalate resin added to improve the adhesion and other properties of the photocurable composition will reduce the reactivity of the photocurable composition and affect its curing rate. Summary of the Invention

[0006] The main objective of this invention is to provide a diallyl phthalate resin-modified compound, its preparation method, and its application, in order to solve the problem of insufficient reactivity of diallyl phthalate resin in the prior art.

[0007] To achieve the above objectives, according to one aspect of the present invention, a diallyl phthalate resin-modified compound is provided, the compound having a weight-average molecular weight of 5000-100000, and the compound containing the structure shown in structural formula I, wherein 1:4 ≤ x:y ≤ 4:1; R1 and R2 each independently represent hydrogen atoms, C1 to C2 atoms, C3 to C4 to C5 to C6 to C7 to C8 to C9 ... 10 Straight-chain or branched alkyl groups, C1-C 10 Alkoxy, C2-C 10 Unsaturated hydrocarbon groups, C3~C 10 cycloalkyl, C2-C 10 Any one of ether group, halogen atom and haloalkyl group.

[0008] Structural Formula I Furthermore, R1 is selected from hydrogen atom, C1-C6 straight-chain or branched alkyl, C1-C6 alkoxy, C2-C6 ether group, halogen and C1-C6 haloalkyl group; and / or, R2 is selected from hydrogen atom or methyl; and / or, 1:1.5 ≤x:y≤ 2:1.

[0009] Furthermore, R1 is selected from hydrogen atom, C1-C2 straight-chain alkyl, C2-C3 ether group, C1-C2 haloalkyl group, and R2 is selected from hydrogen atom or methyl, and 1:1 ≤x:y≤ 1.3:1.

[0010] Furthermore, the weight-average molecular weight of the compound is 40,000-70,000, and preferably, the structure of the compound is selected from any of the following: , , , , , , , , , , , , , , , , and .

[0011] According to another aspect of the present invention, a method for preparing a compound as described above is provided, the method comprising the following steps: Step S1, under an inert gas protective atmosphere, an organic solvent, diallyl phthalate resin, and an oxetane polymer are stirred and mixed uniformly, and the mixture is heated to reflux to obtain a pre-dehydrated reaction solution; the oxetane polymer is a compound represented by structural formula II; Step S2, a catalyst is slowly added, and the mixture is heated to reflux temperature to carry out the reaction, thereby obtaining a crude solution of diallyl phthalate resin-modified compound; Step S3, the target product is separated from the crude solution of diallyl phthalate resin-modified compound to obtain the compound; Structural Form II In the above structural formula II, R1 and R2 independently represent hydrogen atoms and C1 to C2 atoms. 10 Straight-chain or branched alkyl groups, C1-C 10 Alkoxy, C2-C 10 Unsaturated hydrocarbon groups, C3~C 10 cycloalkyl, C2-C 10 Any one of ether group, halogen atom and haloalkyl group, with a molecular weight of 250~1100 for structural formula II.

[0012] Further, in step S1, the mass ratio of diallyl phthalate resin to oxetine polymer is 10:1 to 1:10; preferably 3:1 to 1:10. Preferably, the weight-average molecular weight of diallyl phthalate resin is 5,000 to 80,000, more preferably 10,000 to 60,000, and even more preferably 30,000 to 50,000.

[0013] Further, in step S1, the inert gas includes any one or more of nitrogen, argon, helium, krypton, and neon; and / or, the organic solvent includes any one or more of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane, and trichloromethane. Preferably, the viscosity of the oxobutane polymer at 25°C is 5–500 cps, more preferably 10–300 cps, and even more preferably 20–200 cps.

[0014] Further, in step S2, the catalyst includes any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate, and tribenzyl aluminate; Preferably, the reflux temperature in steps S1 and S2 is 25–250°C, more preferably 60–180°C, and even more preferably 80–160°C.

[0015] Further, step S3 specifically includes the following steps: Step S31, the crude solution of diallyl phthalate resin modified compound is subjected to vacuum distillation to obtain a concentrated solution of diallyl phthalate resin modified compound; preferably, the pressure of vacuum distillation is 10-500 mbar and the temperature is 25-120℃; more preferably, the solvent distilled off by vacuum distillation is recovered and reused; Step S32, the concentrated solution of diallyl phthalate resin modified compound is crystallized and washed with a poor solvent, filtered and dried to obtain the compound; preferably, the poor solvent includes any one or more of methanol, ethanol, diethyl ether, ethylene glycol monomethyl ether, n-hexane, n-octane and petroleum ether.

[0016] According to another aspect of the present invention, a curable resin composition is provided, the curable resin composition comprising any of the diallyl phthalate resin modified compounds described above.

[0017] Furthermore, the above-mentioned curable resin composition further includes a photocurable resin, a photopolymerizable monomer, and a photopolymerization initiator; preferably, by weight, the photocurable resin is 20-50 parts, the photopolymerizable monomer is 20-50 parts, the photopolymerization initiator is 0.1-10 parts, and the diallyl phthalate modified resin compound is 0.5-10 parts.

[0018] According to one aspect of the present invention, a photocurable product is provided, which contains any of the compounds described above or any of the curable resin compositions described above; preferably, the photocurable product is any one or more of 3D printed articles, inks, coatings or adhesives.

[0019] By applying the technical solution of this invention, a type of low-viscosity oxobutane polymer with high reactivity is attached to diallyl phthalate resin to obtain a diallyl phthalate resin-modified compound. This diallyl phthalate resin-modified compound not only possesses the solvent resistance, water resistance, and scratch resistance of diallyl phthalate resin, but also has high reactivity, allowing it to be cured under various energy conditions. In particular, it is easy to light-cur or heat-cur, and the curing rate is fast. This solves the problem of insufficient reactivity of diallyl phthalate resin in the prior art, which affects the curing rate. Attached Figure Description

[0020] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 For raw material 1(a) in Example 1 of the present invention 1 H-NMR spectrum; Figure 2 For raw material 1(b) in Example 1 of the present invention 1 H-NMR spectrum; Figure 3 For raw material 1 (c) in Example 1 of the present invention 1 H-NMR spectrum; Figure 4 A schematic diagram of a solvent-resistant wiping device for performance evaluation according to the present invention is shown; Figure 5 A schematic cross-sectional view of the wiping head of a solvent-resistant wiping device for performance evaluation according to the present invention is shown.

[0021] The above figures include the following reference numerals: 1. Controller; 2. Sliding arm; 3. Wiping head; 4. Test bench; 5. Template clamp; 31. Upper nut (fixing the wiping head); 32. Wiping head inner cavity; 33. Solvent guide hole; 34. Lower nut (fixing the degreased cotton); 35. Contact surface. Detailed Implementation

[0022] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0023] As analyzed in the background section of this application, the prior art suffers from insufficient reactivity of diallyl phthalate resin. To address this issue, this application provides a modified diallyl phthalate resin compound, its preparation method, and its application.

[0024] According to a typical embodiment of this application, a diallyl phthalate resin-modified compound is provided. The compound has a weight-average molecular weight of 5000-100000 and contains the structure shown in structural formula I: in the structural formula, x, y, and z represent the number of corresponding repeating units, where 1:4 ≤ x:y ≤ 4:1, and the number of z has no special requirements, as long as it meets the overall molecular weight requirement; R1 and R2 each independently represent hydrogen atoms, C1~C1~C2 ... 10 Straight-chain or branched alkyl groups, C1-C 10 Alkoxy, C2-C 10 Unsaturated hydrocarbon groups, C3~C 10 cycloalkyl, C2-C 10 Ether groups, halogen atoms, and halogenated hydrocarbon groups.

[0025] Structural Formula I This application links a class of highly reactive, low-viscosity oxobutane polymers to diallyl phthalate resin to obtain a diallyl phthalate resin-modified compound. This diallyl phthalate resin-modified compound not only possesses the solvent resistance, water resistance, and scratch resistance of diallyl phthalate resin, but also exhibits high reactivity, allowing it to be cured under various energy conditions. In particular, it is easy to light-cur or heat-cur, and has a fast curing rate, thus solving the problem of insufficient reactivity of diallyl phthalate resin in the prior art, which affects the curing rate.

[0026] The above structural formula I shows the main functional groups in the diallyl phthalate resin modified compound of this application. Those skilled in the art will understand that the compound may also contain groups of diallyl phthalate resin that have not been modified, that is, the modified compound may also contain groups shown in the following structural formula III: Structural Form III In some embodiments of this application, in the compounds represented by structural formula I above, R1 is selected from hydrogen atoms, C1-C6 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, C2-C6 ether groups, halogens, and C1-C6 haloalkyl groups, resulting in modified diallyl phthalate resins with higher activity. In some embodiments, R2 is selected from hydrogen atoms or methyl groups, and modified diallyl phthalate resins with this structure have more readily available raw materials, are easier to prepare, and also possess good activity. In some embodiments, 1:1.5 ≤ x:y ≤ 2:1, and modified diallyl phthalate resins with this structure not only have higher activity but are also easier to prepare, showing better application prospects.

[0027] In some preferred embodiments, in the compound shown in structural formula I above, R1 is selected from hydrogen atom, C1-C2 straight-chain alkyl, C2-C3 ether group, C1-C2 haloalkyl group, and R2 is selected from hydrogen atom or methyl, and 1:1 ≤x:y ≤ 1.3:1. The modified diallyl phthalate resin obtained is further improved in activity and is easier to prepare and promote.

[0028] In some preferred embodiments, the weight-average molecular weight of the diallyl phthalate resin modified compound is 40,000 to 70,000, and the curing effect is more significantly improved after modification.

[0029] For example, the diallyl phthalate resin-modifying compound described above is selected from any one of the following: , , , , , , , , , , , , , , , , and .

[0030] According to another typical embodiment of this application, a method for preparing a compound as described above is provided, the method comprising the following steps: Step S1, under an inert gas protective atmosphere, an organic solvent, diallyl phthalate resin, and an oxetane polymer are stirred and mixed evenly, and the mixture is heated to reflux to obtain a pre-dehydrated reaction solution, wherein the oxetane polymer is a compound represented by structural formula II, wherein R1 and R2 each independently represent a hydrogen atom, C1 to C2, C3, C4, C5, C6, C7, C8, C9 ... 10 Straight-chain or branched alkyl groups, C1-C 10 Alkoxy, C2-C 10 Unsaturated hydrocarbon groups, C3~C 10 cycloalkyl, C2-C 10 The molecular weight of the structure II is 250-1100, consisting of any one of ether group, halogen atom, and haloalkyl group; Step S2: the catalyst is slowly added and the reaction is carried out at reflux temperature to obtain a crude solution of diallyl phthalate resin modified compound; Step S3: the target product in the crude solution of diallyl phthalate resin modified compound is separated to obtain the compound.

[0031] Structural Form II The above preparation method involves transesterifying a low-viscosity oxetane polymer with high reactivity onto diallyl phthalate resin to obtain a diallyl phthalate resin-modified compound. This modified phthalate resin compound not only possesses the solvent resistance, water resistance, and scratch resistance of diallyl phthalate resin but also exhibits high reactivity, allowing for curing under various energy conditions, particularly easy photocuring or thermal curing, with a fast curing rate. This solves the problem of insufficient reactivity of diallyl phthalate resin in existing technologies, which affects the curing rate. Furthermore, the entire process of the above preparation method is easy to operate, the reaction process is safe and controllable, the cost is low, the yield is high, and it is environmentally friendly, making it extremely valuable for the large-scale commercial production of this diallyl phthalate resin-modified compound.

[0032] The reaction formula for this preparation method is shown below:

[0033] In structural formula II, which represents the structure of oxacyclobutane polymers, R1, R2, and z have the same meanings as the corresponding R1, R2, and z in diallyl phthalate resin-modified compounds. For example, structural formula II has the following structure: , , , , , , , , , , , , , , , , , , and .

[0034] In some embodiments, to facilitate the selection of structurally suitable oxetane polymers, the compounds represented by structural formula II above have a viscosity of 5–500 cps at 25°C, more preferably 10–300 cps, and even more preferably 20–200 cps. Oxetane polymers within the above viscosity range are more conducive to transesterification reactions, and the resulting modified diallyl phthalate resin has higher activity. For example, preferred viscosities are 40 cps, 60 cps, 80 cps, 100 cps, 120 cps, 140 cps, 160 cps, 180 cps, 200 cps, or any range of two such values.

[0035] In the above transesterification reaction, the feeding ratio of each raw material in the transesterification reaction of diallyl phthalate resin and oxetane polymer can be based on the stoichiometric ratio of the reaction, and this application does not limit it. In some embodiments, the mass ratio of diallyl phthalate resin to oxetane polymer is 10:1 to 1:10, preferably 3:1 to 1:10. At this ratio, an appropriate excess of oxetane polymer is beneficial to improving the formation of the target modified compound, and the resulting diallyl phthalate resin modified compound has a better photocuring effect.

[0036] In some embodiments, the weight-average molecular weight of diallyl phthalate resin is 5,000 to 80,000, more preferably 10,000 to 60,000, and even more preferably 30,000 to 50,000. The modified compound has higher activity and better comprehensive properties such as solvent resistance, water resistance and scratch resistance.

[0037] In some embodiments of this application, in step S1 above, the inert gas includes any one or more of nitrogen, argon, helium, krypton, and neon, all of which can facilitate the reaction. The organic solvent can be selected from commonly used organic solvents in the prior art. In some embodiments, the solvent includes any one or more of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane, and trichloromethane. These solvents not only have good dissolving effects on the reactants but also promote the reaction, and have suitable reflux temperatures, allowing the reaction to proceed within a suitable temperature range. Preferably, the viscosity of the oxobutane polymer at 25°C is 5–500 cps, more preferably 10–300 cps, and even more preferably 20–200 cps, which is beneficial for the reaction.

[0038] The catalysts described above can be selected from those commonly used in transesterification reactions in the prior art. In some embodiments of this application, in step S2, the catalysts include any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate, and tribenzyl aluminate, which have better catalytic effects on the above reactions and can further improve the reaction rate and selectivity.

[0039] The reaction temperature of the transesterification can be determined based on the reflux temperature of the solvent. Preferably, in steps S1 and S2, by selecting a suitable solvent, the reflux temperature is set to 25–250°C, more preferably 60–180°C, and even more preferably 80–160°C, which improves the selectivity of the transesterification reaction.

[0040] Step S3 above, for the separation and purification of diallyl phthalate resin-modified compounds, can refer to existing technologies. In some preferred embodiments of this application, step S3 includes: Step S31, subjecting the crude diallyl phthalate resin-modified compound solution to vacuum distillation to obtain a concentrated diallyl phthalate resin-modified compound solution; preferably, the vacuum distillation pressure is 10–500 mbar and the temperature is 25–120°C; more preferably, the solvent distilled off by vacuum distillation is recovered and reused; Step S32, the concentrated diallyl phthalate resin-modified compound solution is crystallized with a poor solvent, washed, filtered, and dried to obtain the compound; wherein, the poor solvent refers to a solvent with low solubility for the target compound, which facilitates its crystallization. In some embodiments, the poor solvent includes any one or more of methanol, ethanol, diethyl ether, ethylene glycol monomethyl ether, n-hexane, n-octane, and petroleum ether, which have good crystallization effects.

[0041] According to another typical embodiment of this application, a curable resin composition is provided, which contains any of the diallyl phthalate resin-modifying compounds described above. The diallyl phthalate resin-modifying compounds not only possess the solvent resistance, water resistance, and abrasion resistance of diallyl phthalate resin, but also exhibit high reactivity, can be cured under various energy conditions, and are particularly easy to light-cur or heat-cur, with a fast curing rate. They can be widely used as prepolymers in curable resin compositions and are suitable for curing under various energy conditions.

[0042] In a typical embodiment, the above-mentioned photocurable resin composition includes a photocurable resin, a photopolymerizable monomer, a photopolymerization initiator, and the above-mentioned diallyl phthalate resin-modified compound. Preferably, by weight, the photocurable resin is 20-50 parts, the photopolymerizable monomer is 20-50 parts, the photopolymerization initiator is 0.1-10 parts, and the diallyl phthalate-modified resin compound is 0.5-10 parts.

[0043] The photocurable resin can be selected from existing technologies, such as any one or more selected from epoxy resins, vinyl ether resins, and amino resin compounds. Preferably, the epoxy resin is selected from any one or more selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, biphenyl type epoxy resins, phenolic varnish type epoxy resins, cresol phenolic varnish type epoxy resins, bisphenol A phenolic varnish type epoxy resins, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy resins, and epoxy compounds having siloxane bonding sites.

[0044] There are no particular restrictions on photopolymerization initiators; any substance capable of initiating double bond polymerization under light conditions can be used. Photopolymerization initiators can be free radical photoinitiators or cationic initiators, such as one or more combinations of benzophenone initiators, triazine initiators, dialkoxyacetophenone initiators, α-hydroxyalkylphenyl ketone initiators, α-aminealkylphenyl ketone initiators, acylphosphine oxide initiators, benzophenone initiators, benzoin initiators, benzoyl initiators, heterocyclic aromatic ketone initiators, and oxime ester photoinitiators. Cationic initiators can be any one or more of thionyl or iodonium salt initiators.

[0045] The photopolymerizable monomers in the above-mentioned photocurable compositions can improve the photosensitivity, crosslinking properties, mechanical strength, and chemical resistance of the photocurable compositions. Any compound with one or more unsaturated bonds within its molecule can be selected as needed, such as oxetane monomers or acrylate monomers. Exemplary examples of the photopolymerizable monomers selected in this invention include: TCM207, TCM208, TCM245 (manufactured by Changzhou Qiangli New Materials), propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, tetrapropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and sorbitol triglyceride. (Meth)acrylic acid adducts of epoxy compounds such as glycidyl ether and glycerol triglycidyl ether; unsaturated organic acids such as maleic acid and their anhydrides; acrylamides such as N-methacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-hydroxymethylacrylamide, N-methylacrylamide, N-ethylmethacrylamide, N-isopropylmethacrylamide, N-hydroxymethylmethacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-dimethylacrylamide, and N,N-diethylmethacrylamide; polyethylene glycol di(meth)acrylate (2-14 ethylenes); trimethylolpropane di(meth)acrylate Esters, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane propoxytri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, polypropylene glycol di(meth)acrylate (propylene group 2-14); dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A polyoxyethylene di(meth)acrylate, bisphenol A dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene di(meth)acrylate, bisphenol A oxyvinyl di(meth)acrylate, polycarboxylic acids (such as phthalic anhydride, etc.). Esterifications of compounds with hydroxyl and olefinic unsaturated groups (such as β-hydroxyethyl methacrylate), methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and other alkyl methacrylates; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, styrene, hydroxystyrene, and other styrene derivatives; N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-vinylimidazole, etc.; the substances listed above can be used alone or in combination.

[0046] Depending on the application requirements of the product, the above-mentioned photocurable composition may also selectively contain colorants, additives and solvents. Preferably, the colorant is 20 to 30 parts by weight, and the additives include one or more of curing agents and leveling agents. Preferably, the additives are 0.1 to 1.0 parts by weight, and the solid content of the photocurable composition is 10% to 30%.

[0047] The aforementioned colorants are commonly used in the art, and their addition can effectively form color filters. Any organic or inorganic pigments commonly used in the art can be selectively used as colorants in this application. These include azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, indoleanthrone pigments, indanone pigments, pyrroledione pigments, etc. The aforementioned pigments can be used individually or in mixtures, depending on the specific requirements of the product.

[0048] Further preferred organic raw materials are listed below, but are not limited to, specific pigments. Compounds with specific color indices (CI) are listed, such as: CI Pigment Orange 1, 3, 11, 13, 14, 15, 16, 17, 20, 24, 3, 53, 55, 60, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 100, 101, 106, 109, 120, 125, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 167, 175, 180, 183, 185; CI Pigment Orange 1, 13, 31, 36, 42, 43, 55, 59, 61, 65, 71; CI pigment purple 1, 14, 19, 23, 29, 30, 36, 37, 38, 39, 40; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 18, 19, 21, 23, 30, 31, 37, 38, 40, 42, 48, 53:1, 57, 57:2, 60:1, 83, 97, 105, 122, 144, 166, 176, 180, 192, 202, 206, 207, 208, 215, 224, 242, 254, 255, 264, 265; CI Pigment Blue 1, 2, 15, 15:3, 15:6, 16, 21, 22, 60, 64, 66; CI Pigment Green 7, 10, 15, 25, 36, 47, 48; CI Pigment Brown 23, 25, 26, 28; CI Pigment Black 1 and 7, etc.

[0049] The above-mentioned photocurable compositions can be enhanced with additives to improve certain properties. Commonly used additives include fillers, curing agents, leveling agents such as BYK307 and BYK333, adhesion promoters, antioxidants, and UV absorbers, but are not limited to these.

[0050] According to another typical embodiment of this application, a photocurable product is provided, which contains any of the diallyl phthalate resin modified compounds or any of the curable resin compositions described above. This photocurable product exhibits excellent solvent resistance, water resistance, and scratch resistance, and also has high reactivity and a fast curing rate. Preferably, the photocurable product is any one or more of 3D printed products, inks, coatings, or adhesives.

[0051] The beneficial effects of the technical solution of this application will be further illustrated below with reference to embodiments and comparative examples.

[0052] In this application, unless otherwise stated, the viscosity at 25°C was determined by a viscosity analyzer (model: DV1, BROOKFIELD), and the weight-average molecular weight Mw was tested by gel chromatography (instrument model: LC-20AD, Shimadzu, Japan), and the test results were obtained using a standard polystyrene calibration curve.

[0053] Preparation Examples Example 1 The reaction equation is as follows:

[0054] Nitrogen gas was introduced into a 500mL four-necked flask, and 80g of raw material 1(a) (manufactured by Daiso Corporation, Japan, DAP-A) was added under nitrogen atmosphere. The mixture was prepared by stirring 680g of raw material 1(b) (a self-made product, prepared by the method described in patent application number 202110359249.1, with a weight-average molecular weight of approximately 410 and a viscosity of 41.16 cps at 25°C) and 200ml of toluene. The mixture was stirred and refluxed at 120°C. Water was removed from the system using a water separator. 7.6g of tetraethyl titanate was slowly added dropwise. After the addition was complete, the mixture was refluxed at 135°C for 24 hours, and the tail gas was absorbed with 200ml of pure water. After the reaction was complete, the temperature was lowered to 80°C, and the solvent was removed by vacuum distillation at 100mbar. The mixture was cooled to room temperature, and the resulting liquid was added to 500ml of methanol and stirred to crystallize for 1 hour. The crude product was filtered and washed with 500ml of methanol. After filtration and drying, 112g of a white solid was obtained. The solid was determined by gel permeation chromatography. The structure of product 1(c) was determined by proton nuclear magnetic resonance spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed the results: 4.2 The peak at 4.5 ppm indicates the hydrogen atom in the quaternary epoxy structural unit of raw material 1(b), 7.3 ppm. The peak at 7.7 ppm indicates the hydrogen atoms on the benzene ring in the side chain structure of raw material (a). The peak values ​​of raw materials 1(a), 1(b), and target product 1(c) are... 1 The H-NMR spectra are as follows: Figure 1 , Figure 2 and Figure 3 As shown.

[0055] Example 2 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1(b) with 2(b) (weight-average molecular weight approximately 390, viscosity at 25°C 37.05 cps), to obtain 108 g of product 2(c) (white solid). The structure of product 2(c) was determined by hydrogen nuclear magnetic resonance spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed: 4.2 The peak at 4.4 ppm indicates the hydrogen atom in the quaternary epoxy structural unit of raw material 2(b). 7.4 The peak at 7.7 ppm indicates the hydrogen atom on the benzene ring in the side chain structure of reactant (a). The structures of reactant 2 (b) and product 2 (c) are as follows:

[0056] Example 3 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1(b) with 3(b) (weight-average molecular weight approximately 310, viscosity at 25°C 28.26 cps), to obtain 106 g of product 3(c) (white solid). The structure of product 3(c) was determined by hydrogen nuclear magnetic resonance spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed: 4.2 The peak at 4.5 ppm indicates the hydrogen atom in the quaternary epoxy structural unit of raw material 3(b), 7.3 ppm. The peak at 7.6 ppm indicates the hydrogen atom on the benzene ring in the side chain structure of reactant (a). The structures of reactant 3(b) and product 3(c) are as follows:

[0057] Example 4 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1 (II) with 4 (b) (weight-average molecular weight approximately 320, viscosity at 25°C 29.95 cps), to obtain 105 g of product 4 (c) (white solid). The structure of product 4(c) was determined by hydrogen nuclear magnetic resonance spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed: 4.2 The peak at 4.4 ppm indicates the hydrogen atom in the 4(b) quaternary epoxy structural unit of the raw material. 7.3 The peak at 7.7 ppm indicates the hydrogen atom on the benzene ring in the side chain structure of reactant (a). The structures of reactant 4(b) and product 4(c) are as follows:

[0058] Example 5 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1(b) with 5(b) (weight-average molecular weight approximately 480, viscosity at 25°C 52.00 cps), to obtain 113 g of product 5(c) (white solid). The structure of product 5(c) was determined by hydrogen nuclear magnetic resonance spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed: 4.2 The peak at 4.5 ppm indicates the hydrogen atom in the 5(b) quaternary epoxy structural unit of the raw material. 7.3 The peak at 7.7 ppm indicates the hydrogen atom on the benzene ring in the side chain structure of reactant (a). The structures of reactant 5(b) and product 5(c) are as follows:

[0059] Example 6 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1(b) with 6(b) (weight-average molecular weight approximately 400, viscosity at 25°C 38.00 cps), to obtain 102 g of product 6(c) (white solid). The structure of product 6(c) was determined by hydrogen nuclear magnetic resonance spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed: 4.2 The peak at 4.4 ppm indicates the hydrogen atom in the quaternary epoxy structural unit of raw material 6(b). 7.2 The peak at 7.7 ppm indicates the hydrogen atom on the benzene ring in the side chain structure of feedstock (a). The structures of feedstock 6(b) and product 6(c) are as follows:

[0060] Example 7 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1(b) with 7(b) (weight-average molecular weight approximately 530, viscosity at 25°C 58.12 cps), to obtain 105 g of product 7(c) (white solid). The structures of raw material 7(b) and product 7(c) are as follows:

[0061] Example 8 Repeat the steps shown in Example 1, keeping other conditions unchanged. Replace raw material 1(a) with 8(a) (DAP-A manufactured by Daiso Corporation, Japan). (x:y≈1.3:1.0), yielding 108g of product 8(c) (white solid). …). The structure of product 8(c) was determined by 1H NMR spectroscopy. 1 H-NMR (CDCl3, 400MHz) confirmed: 4.2 The peak at 4.5 ppm indicates the hydrogen atom in the quaternary epoxy structural unit of raw material 8(b). 7.2 The peak at 7.7 ppm indicates the hydrogen atom on the benzene ring in the side chain structure of reactant 8(a). The structures of reactant 8(a) and product 8(c) are as follows:

[0062] Example 9 The difference from Example 1 is that the amount of raw material 1(b) added is 40g, yielding 95g of product 9(c) (a white solid). …).

[0063] Example 10 The difference from Example 1 is that the amount of raw material 1(b) added is 6g, yielding 57g of product 10(c) (a white solid). …).

[0064] Performance Evaluation UV-curable inks refer to inks in which the photosensitizer in the ink initiates the polymerization of monomers in the ink binder into polymers under ultraviolet light, causing the ink to form a film and dry. UV-curable inks for each test example and comparative example were prepared according to the formulations shown in Table 1. The units for each component in Table 1 are in grams. All test examples used UV-curable ink bases with the same composition and proportions, differing only in the added modifiers. Comparative Example 1 differed from the test examples in that no modifier was added. Comparative Example 2 differed from the test examples in that the modifier was replaced with diallyl phthalate resin and oxetane polymer (i.e., raw material 1(a) and raw material 1(b)) that had not undergone transesterification. Comparative Example 3 differed from the test examples in that the modifier was replaced with unmodified diallyl phthalate resin (i.e., raw material 1(a)).

[0065] Table 1

[0066] Table E represents the diallyl phthalate resin-modified compound prepared in the above examples. The specific components selected for the other components are as follows: A: Epoxy 828 resin (Jiangyin Wanqian Chemical Co., Ltd.) B: TTA21 resin (Jiangsu Taitel New Material Technology Co., Ltd.) C: TCM207() D: Black pigment paste (a pre-prepared dispersion of carbon black) F: DAP resin (Daiso Chemicals & Industrial Co., Ltd., Japan) G: Raw material 1 (b) H1: Triphenylthionium hexafluorophosphate H2: PSS306 (10-diethoxy-2-ethylanthracene) 1. Curing speed test The ink to be tested was coated onto a PET film (FP2 industrial film from Lucky Group) using a 10μm wire rod. A 385nm UVLED conveyor belt exposure machine (Shenzhen Runwo Electromechanical Co., Ltd.) was used as the radiation source, with a UVLED irradiation intensity of 20W / cm². 2 After exposure to sunlight, the drying time of paint films and putty films was determined according to GB1728-1979, using the touch test method. The coating was lightly touched with a finger; complete curing was confirmed when the surface was smooth, non-sticky, and left no fingerprints upon pressing. Curing speed was expressed as the maximum exposure energy required to achieve complete curing, in mJ / cm². 2 .

[0067] 2. Solvent resistance wiping test The solvent resistance was tested according to Method A of GB / T23989-2009, "Determination of Solvent Resistance of Coatings by Wiping Test". A solvent resistance wiping tester (Biaogeda Precision Instruments (Guangzhou) Co., Ltd.) was used. The solvent resistance wiping tester is attached. Figure 4 and Figure 5 As shown. Instrument parameters: wiping stroke: 12cm±0.5cm; contact surface diameter: 14mm±0.5mm; load on test plate: 1000g±10g; wiping frequency: (60±5) reciprocating wipes per minute. Specific implementation method is as follows: The experiment was conducted at room temperature of 18℃~27℃. A suitable amount of degreased cotton was moistened with methyl ethyl ketone (MEK) solvent, squeezed until no solvent dripped, and wrapped around the contact surface 35 of the wiping head 3. Then, a suitable amount of degreased cotton was placed into the inner cavity 32 and solvent guide hole 33 of the wiping head, and a suitable amount of solvent was dripped in. The upper and lower nuts 34 were tightened to secure the degreased cotton, and the upper nut 31 was tightened to fix the wiping head 3 onto the sliding arm 2 of the solvent-resistant wiping instrument. The sample clamp 5 was fixed on the test bench 4, and its position was adjusted so that the wiping head 3 could fall in the middle of the sample clamp 5. The controller 1 controlled the sliding arm 2 to drive the wiping head 3 to wipe until the area 8cm in the middle of the sample clamp 5 was exposed. The number of wiping cycles was recorded (one reciprocating motion was counted as one cycle), and the experiment was stopped.

[0068] 3. Coating abrasion resistance test The abrasion resistance of paints and varnishes was determined according to the "GB / T1768-2006 Determination of Abrasion Resistance of Paints and Varnishes - Rotating Rubber Grinding Wheel Method". The specific implementation method is as follows: At 23℃±2℃ and 50%±5% relative humidity, a 500g weight is added to a rubber grinding wheel, and then the paint film is rubbed with the rubber grinding wheel fixed on the abrasion tester. The abrasion resistance of the paint film is represented by the amount of mass loss of the paint film after 100 friction cycles.

[0069] The test results are shown in Table 2: Table 2

[0070] As can be seen from the performance evaluation results in Table 2, the diallyl phthalate resin modified compound of the present invention has high reactivity, requires low energy for complete curing, and can significantly improve the solvent resistance and wear resistance of the cured coating. Moreover, the process cost is relatively low, and it has strong application prospects.

[0071] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A diallyl phthalate resin-modified compound, characterized in that, The compound has a weight-average molecular weight of 5,000 to 100,000, and the diallyl phthalate resin-modified compound contains the structure shown in structural formula I: Structural Formula I Where 1:4 ≤x:y≤ 4:1, R1 independently represents hydrogen atoms, C1~C 10 Straight-chain or branched alkyl groups, C1-C 10 Alkoxy, C3~C 10 cycloalkyl, C2-C 10 Any one of ether group and haloalkyl group; R2 is selected from hydrogen atom or methyl.

2. The diallyl phthalate resin-modified compound according to claim 1, characterized in that, R1 is selected from hydrogen atoms, C1-C6 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, C2-C6 ether groups, halogens, and C1-C6 haloalkyl groups; And / or, 1:1.5≤x:y≤2:

1.

3. The diallyl phthalate resin-modified compound according to claim 2, characterized in that, R1 is selected from hydrogen atom, C1-C2 straight-chain alkyl, C2-C3 ether group, C1-C2 haloalkyl group, and R2 is selected from hydrogen atom or methyl, and 1:1≤x:y≤1.3:

1.

4. The diallyl phthalate resin-modified compound according to claim 1, characterized in that, The weight-average molecular weight of the diallyl phthalate resin-modified compound is 40,000-70,000.

5. The diallyl phthalate resin-modified compound according to claim 4, characterized in that, The structure of the diallyl phthalate resin-modified compound is selected from any one of the following: , , , , , , , , , , , , , , , , and .

6. A method for preparing the diallyl phthalate resin-modified compound according to any one of claims 1 to 5, characterized in that, Includes the following steps: Step S1: Under an inert gas protective atmosphere, the organic solvent, diallyl phthalate resin, and oxetane polymer are stirred and mixed evenly, then heated to reflux to obtain a pre-dehydrated reaction solution; the oxetane polymer is a compound represented by structural formula II. Structural Form II Where R1 independently represents a hydrogen atom, C1 to C1, and C2 are atoms of hydrogen. 10 Straight-chain or branched alkyl groups, C1-C 10 Alkoxy, C3~C 10 cycloalkyl, C2-C 10 The R2 is selected from either an ether group or a haloalkyl group, wherein the molecular weight of the structural formula II is 250 to 1100. Step S2: The catalyst is slowly added and the temperature is raised to reflux to carry out the reaction, resulting in a crude solution of diallyl phthalate resin modified compound. Step S3: Separate the target product from the crude solution of the diallyl phthalate resin-modified compound to obtain the diallyl phthalate resin-modified compound.

7. The preparation method according to claim 6, characterized in that, In step S1, the mass ratio of diallyl phthalate resin to oxetine polymer is 10:1 to 1:

10.

8. The preparation method according to claim 7, characterized in that, In step S1, the mass ratio of diallyl phthalate resin to oxobutane polymer is 3:1 to 1:

10.

9. The preparation method according to claim 7, characterized in that, The diallyl phthalate resin has a weight-average molecular weight of 5,000 to 80,000.

10. The preparation method according to claim 9, characterized in that, The diallyl phthalate resin has a weight-average molecular weight of 10,000 to 60,000.

11. The preparation method according to claim 10, characterized in that, The diallyl phthalate resin has a weight-average molecular weight of 30,000 to 50,000.

12. The preparation method according to claim 6, characterized in that, In step S1, the inert gas includes any one or more of nitrogen, argon, helium, krypton, and neon. And / or, the organic solvent includes any one or more of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane, and trichloromethane.

13. The preparation method according to claim 12, characterized in that, The viscosity of the oxobutane polymer at 25°C is 5–500 cps.

14. The preparation method according to claim 13, characterized in that, The viscosity of the oxobutane polymer at 25°C is 10–300 cps.

15. The preparation method according to claim 14, characterized in that, The viscosity of the oxobutane polymer at 25°C is 20–200 cps.

16. The preparation method according to claim 6, characterized in that, In step S2, the catalyst includes any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate, and tribenzyl aluminate.

17. The preparation method according to claim 16, characterized in that, The reflux temperature in steps S1 and S2 is 25–250°C.

18. The preparation method according to claim 17, characterized in that, The reflux temperature in steps S1 and S2 is 60–180°C.

19. The preparation method according to claim 18, characterized in that, The reflux temperature in steps S1 and S2 is 80–160°C.

20. The preparation method according to claim 6, characterized in that, Step S3 specifically includes the following steps: Step S31: The crude solution of diallyl phthalate resin modified compound is subjected to vacuum distillation to obtain a concentrated solution of diallyl phthalate resin modified compound. Step S32: The concentrated solution of the diallyl phthalate resin modified compound is crystallized and washed with a poor solvent, filtered and dried to obtain the diallyl phthalate resin modified compound.

21. The preparation method according to claim 20, characterized in that, The pressure of the vacuum distillation is 10–500 mbar, and the temperature is 25–120 °C.

22. The preparation method according to claim 20, characterized in that, The solvent distilled off under reduced pressure is recovered and reused.

23. The preparation method according to claim 20, characterized in that, The undesirable solvents include any one or more of methanol, ethanol, diethyl ether, ethylene glycol monomethyl ether, n-hexane, n-octane, and petroleum ether.

24. A curable resin composition, characterized in that, The phthalate diallyl resin modified compound included in any one of claims 1 to 5.

25. The curable resin composition according to claim 24, characterized in that, It also includes photocurable resins, photopolymerizable monomers, and photopolymerization initiators.

26. The curable resin composition according to claim 25, characterized in that, By weight, the photocurable resin is 20-50 parts, the photopolymerizable monomer is 20-50 parts, the photopolymerization initiator is 0.1-10 parts, and the diallyl phthalate resin-modifying compound is 0.5-10 parts.

27. A photocurable product, characterized in that, The light-curing product contains a diallyl phthalate resin-modified compound as described in any one of claims 1 to 5 or a curable resin composition as described in any one of claims 24 to 26.

28. The photocurable product according to claim 27, characterized in that, The photocurable product is any one or more of 3D printed products, inks, coatings, or adhesives.

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