Long-lasting fragrance ink and preparation method thereof

Abstract

The present invention provides a kind of ink with lasting fragrance and preparation method thereof, belong to the field of ink technology, the ink with lasting fragrance comprises the following raw materials in parts by weight: 20-40 parts of tripropylene glycol diacrylate, 10-20 parts of trimethylolpropane triacrylate, 20-50 parts of polyurethane acrylate, 1-5 parts of silicone acrylate, 4-6 parts of photoinitiator, 1-5 parts of active amine co-initiator, 3-5 parts of fragrance sustained-release capsule, 0.3-0.5 parts of defoamer, 5-15 parts of solvent; wherein, the fragrance sustained-release capsule is composed of an oil phase consisting of plant essential oil, polylactic acid-co-glycolic acid copolymer, PCL-PEG grafted cyclodextrin and ethyl acetate, and an aqueous phase consisting of polyvinyl alcohol in water, and is made by high-pressure homogenization, rotary evaporation and drying. The ink fragrance prepared by the present invention lasts for a long time and has the characteristics of good stability, strong adhesion, fast curing, scratch resistance, and green environmental protection.

Description

Technical Field

[0001] The invention belongs to the technical field of inks, and in particular relates to an ink with a long-lasting fragrance and a preparation method thereof. Background Art

[0002] With the packaging industry's growing demand for anti-counterfeiting features and sensory experiences, the application of anti-counterfeiting inks in the printing industry is becoming increasingly widespread. Traditional anti-counterfeiting methods, such as laser holograms and QR codes, while able to achieve visual security, often suffer from limitations such as easy duplication or the need for specialized equipment for identification. In contrast, anti-counterfeiting inks leverage the inherent properties of the material, such as optical color change, temperature sensitivity, and scent marking, to integrate anti-counterfeiting features directly into the printing process. This achieves both covert and intuitive functionality, making them particularly suitable for packaging of high-value-added products such as tobacco and pharmaceuticals. Specifically, the core function of anti-counterfeiting inks is to verify authenticity through differences in physical or chemical properties. For example, microencapsulated scented inks encapsulate essential oils within a polymer material, releasing their scent through friction or pressure, creating a unique "olfactory anti-counterfeiting" mark. This approach not only elevates the technical level of anti-counterfeiting but also enhances interactivity by enhancing the consumer's sensory experience.

[0003] At present, there are mainly the following methods to achieve anti-counterfeiting printing: First, the anti-counterfeiting effect is achieved through force-induced deformation, force-induced heating or force-induced sound generation, but the mechanical properties of the material are required to be high, and in actual application, the recognition accuracy may be affected by the instability of the external force; the second is to use thermochromic or thermoluminescent materials to change the color or luminescence characteristics when the temperature changes, but there is a problem of insufficient durability, especially in extreme temperature environments, the color-changing materials are prone to failure or performance degradation; the third is to achieve anti-counterfeiting function through electrochromism or electroluminescence, but because it requires complex circuit system support, the cost is high and the requirements for printing equipment are harsh, which limits its large-scale application; the fourth is to rely on photochromism, fluorescence or laser holography and other technologies. Although it has a high anti-counterfeiting effect and intuitiveness, some optical materials are easy to imitate, which reduces the anti-counterfeiting reliability; in addition, although the ink can be given unique properties through carbon dot preparation and nanomaterial doping, the preparation process is complicated, the process conditions are strict, and there may be environmental pollution problems.

[0004] In order to improve the performance of anti-counterfeiting inks, improvements can be made by optimizing material formulations, improving preparation processes, and introducing new functional materials. In terms of material formulation, the fragrance release time can be prolonged by enhancing the stability of the polymer carrier, while improving the ink's scratch resistance and printing feel; in the preparation process, the use of more sophisticated microencapsulation technology can effectively reduce the volatilization loss of essential oils during storage and transportation, thereby increasing the fragrance's durability; and the functional particles can be evenly dispersed in the ink system using nanotechnology, thereby further improving its overall performance. However, the above methods still have some shortcomings. For example, the aging characteristics of polymer materials can cause the fragrance to significantly weaken over time, resulting in poor durability. When solidified on non-absorbent materials such as metal films and plastics, the adhesion decreases and the ink is easily de-inked. Therefore, there is an urgent need for a new long-lasting fragrance ink and its preparation method, which not only has strong adhesion and can ensure the stability and durability of fragrance release, but also has a simple preparation method that is easy to promote and apply. Summary of the Invention

[0005] The purpose of the present invention is to provide an ink with a long-lasting fragrance. By adopting a specific silicone acrylate, synergistically acting with polyurethane acrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate, and adding a homemade fragrance sustained-release capsule, the ink not only has a long-lasting fragrance but also has the characteristics of good stability, strong adhesion, and fast curing.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides an ink with a long-lasting fragrance, which comprises the following raw materials in parts by weight:

[0008] 20-40 parts of tripropylene glycol diacrylate, 10-20 parts of trimethylolpropane triacrylate, 20-50 parts of polyurethane acrylate, 1-5 parts of silicone acrylate, 4-6 parts of photoinitiator, 1-5 parts of active amine co-initiator, 3-5 parts of fragrance sustained-release capsules, 0.3-0.5 parts of defoaming agent, and 5-15 parts of solvent.

[0009] Preferably, the preparation method of the organosilicon acrylate comprises the following steps:

[0010] Alkylbenzene sulfonate (e.g., sodium dodecylbenzenesulfonate), alkyl glucoside (e.g., APG-0810), and octamethylcyclotetrasiloxane are added to water, heated and stirred, and then circulated using a high-pressure homogenizer to obtain an emulsified intermediate liquid; the emulsified intermediate liquid is adjusted to acidity and heated and stirred, and then (methacryloyloxymethyl)methyldiethoxysilane is added and continued to be stirred, cooled, and the pH is adjusted (e.g., to neutral) to obtain an alkenyl polysiloxane emulsion;

[0011] Persulfate (such as ammonium persulfate) and acrylic acid monomer are sequentially added to alkenyl polysiloxane emulsion, heated for reaction, and cooled to obtain polymer emulsion; anhydrous ethanol is added to the polymer emulsion to break the emulsion, centrifuged, and the precipitate is collected and dried to obtain silicone acrylate.

[0012] By adding the aforementioned organosilicon acrylate to the ink formulation, the present invention achieves a synergistic effect with polyurethane acrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate, significantly improving the ink's overall properties, including adhesion and gloss. This mechanism of action stems from the synergistic effect of the dual characteristics of its molecular structure and interfacial behavior.

[0013] In the preparation process of the organosilicon acrylate, the present invention first uses octamethylcyclotetrasiloxane and (methacryloyloxymethyl)methyldiethoxysilane as organosilicon segments of precursors to form a polysiloxane network through hydrolysis and condensation, giving the material low surface energy and excellent flexibility. This characteristic drives molecules to migrate to the coating surface during the ink curing process, forming a silicon-rich surface layer, significantly reducing the interfacial energy difference between the ink and the plastic substrate (such as PET, PP), thereby enhancing wettability and anchoring effect. Secondly, the acrylate monomer used in the present invention is a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate, which is generated through free radical copolymerization to form a rigid skeleton with a high cross-linking density. This rigid and flexible interpenetrating network structure can not only release internal stress through the deformation of the siloxane chain to avoid cracking, but also form hydrogen bonds or chemical bonds with the substrate surface through the strong polar groups (ester groups, hydroxyl groups) of the acrylate, thereby improving adhesion. In addition, the siloxane chain tends to form a micron-scale domain structure during the phase separation process, and the difference in its refractive index with that of the acrylic resin is controlled within a very small range. This moderate refractive index gradient can reduce light scattering, thereby improving gloss; the long-chain ethoxy group provided by ethoxylated trimethylolpropane triacrylate can act as an internal plasticizer, further balancing the cross-linking density and flexibility, and preventing brittle peeling caused by high hardness.

[0014] Preferably, the weight ratio of the alkylbenzene sulfonate, alkyl glucoside, octamethylcyclotetrasiloxane, and (methacryloyloxymethyl)methyldiethoxysilane is 1-3:0.5-1.5:10-15:2-4; and the weight ratio of the alkenyl polysiloxane emulsion, persulfate, and acrylic acid monomer is 40-60:0.1-0.3:15-20.

[0015] Preferably, the acrylic monomer is a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 3-5:1.

[0016] Preferably, the pressure of the high-pressure homogenizer is 40-60 MPa, and the cycle treatment is 3-5 times.

[0017] Furthermore, the preparation method of the organosilicon acrylate comprises the following steps:

[0018] 1-3 parts of sodium dodecylbenzenesulfonate, 0.5-1.5 parts of alkyl polyglycoside APG-0810, and 10-15 parts of octamethylcyclotetrasiloxane, by weight, are added to 80-100 parts of water, stirred at 30-40° C. and 150-300 rpm for 5-15 minutes, and then circulated through a high-pressure homogenizer for 3-5 times at a pressure of 40-60 MPa to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid is adjusted to 3.0-4.0, stirred at 70-75° C. and 100-300 rpm for 1-3 hours, and then 2-4 parts of (methacryloyloxymethyl)methyldiethoxysilane are added and stirring is continued for 5-8 hours. The mixture is cooled to room temperature and the pH value is adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0019] To 40-60 parts of alkenyl polysiloxane emulsion, 0.1-0.3 parts of ammonium persulfate and 15-20 parts of acrylic acid monomer are sequentially added at 80-90° C. and nitrogen atmosphere, and the mixture is reacted for 4-6 hours, and then cooled to room temperature to obtain a polymer emulsion; 2-5 times the volume of anhydrous ethanol is added to the polymer emulsion, and the mixture is stirred at 450-600 rpm to break the emulsion for 0.5-2 hours, centrifuged, and the precipitate is collected and dried to obtain silicone acrylate.

[0020] Preferably, the method for preparing the flavored sustained-release capsules comprises the following steps:

[0021] Hydroxypropyl-β-cyclodextrin is added to an ethanol aqueous solution and heated with stirring, followed by the addition of sodium hydroxide and 2-ethylhexyl glycidyl ether, stirred for reaction, cooled, the pH adjusted (e.g., to neutral), the addition of cold ether to precipitate, centrifuged, and dried to obtain an alkyl-modified cyclodextrin; the alkyl-modified cyclodextrin and polycaprolactone-polyethylene glycol are added to dimethyl sulfoxide and heated with stirring, followed by the addition of dicyclohexylcarbodiimide for reaction, the addition of cold ether to precipitate, centrifuged, and dried to obtain a PCL-PEG grafted cyclodextrin;

[0022] Plant essential oil and polylactic acid-glycolic acid copolymer are added to ethyl acetate and stirred, and then PCL-PEG grafted cyclodextrin is added and stirred to obtain an oil phase; polyvinyl alcohol is added to water and stirred to obtain an aqueous phase; the oil phase is added to the aqueous phase, and then circulated through a high-pressure homogenizer, and the ethyl acetate is recovered by rotary evaporation, centrifuged, and dried to obtain flavor sustained-release capsules.

[0023] Furthermore, the present invention utilizes the aforementioned self-made sustained-release fragrance capsules instead of directly adding essential oils and other flavoring agents, further improving the ink's fragrance stability and prolonging its scent. First, the alkyl-modified cyclodextrin is grafted with hydrophobic C8-C10 long chains via a ring-opening reaction of the epoxy groups of 2-ethylhexyl glycidyl ether, significantly enhancing the hydrophobic binding capacity of the β-cyclodextrin cavity. This allows the essential oil to be better encapsulated within the cyclodextrin cavity through van der Waals forces and hydrophobic interactions, forming a complex. Secondly, the grafting of polycaprolactone-polyethylene glycol block copolymer introduces amphiphilic interface regulation ability. The polycaprolactone chain segments are physically entangled with the alkyl chains of cyclodextrin through crystallization drive to form a dynamic hydrophobic network; while the polyethylene glycol segments stretch in the aqueous phase to form a spatial steric hindrance layer, and the dual effects inhibit the outward migration of essential oil molecules; in the emulsion preparation stage, the hydrophobic segments of polylactic acid-glycolic acid copolymer and PCL-PEG grafted cyclodextrin form an interpenetrating network through π-π stacking and hydrogen bonding, constituting the second layer of sustained-release barrier, whose degradation rate is regulated by environmental humidity and pH, and the embedded essential oil is gradually released by breaking the ester bond. High-pressure homogenization controls the particle size of the oil phase droplets in the nanometer range, and uses interfacial tension to make the composite film evenly cover the surface of the droplets, forming a dense core-shell structure protective layer. In addition, the adsorption of polyvinyl alcohol at the oil-water interface forms a third hydration barrier, which locks water through a hydrogen bond network to reduce oxygen permeability and inhibit the oxidation and deterioration of essential oils. When the ink is subjected to stimuli such as friction or temperature, the microcrack expansion of the PLGA shell and the viscoelastic deformation of PCL, as well as the gradual dissociation of the cyclodextrin cavity, provide long-term sustained release, effectively extending the fragrance release time.

[0024] Preferably, the weight ratio of the hydroxypropyl-β-cyclodextrin and 2-ethylhexyl glycidyl ether is 4-6:2-5; the weight ratio of the alkyl-modified cyclodextrin and polycaprolactone-polyethylene glycol is 4-6:1-3; the weight ratio of the plant essential oil to polylactic acid-glycolic acid copolymer, PCL-PEG grafted cyclodextrin, and polyvinyl alcohol is 5-15:1-3:5-10:0.5-2.

[0025] Preferably, the plant essential oil is any one of rose essential oil, lemon essential oil, lavender essential oil, grapefruit essential oil, and peony essential oil.

[0026] Preferably, the pressure of the high-pressure homogenizer is 40-60 MPa, and the cycle treatment is 3-5 times.

[0027] Preferably, the temperature of the rotary evaporation is 45-55° C. and the vacuum degree is 150-300 mbar.

[0028] Furthermore, the preparation method of the flavor sustained-release capsule comprises the following steps:

[0029] By weight, 4-6 parts of hydroxypropyl-β-cyclodextrin were added to 80-120 parts of 50-65 wt% ethanol aqueous solution, stirred at 40-50 ° C and 200-400 rpm for 10-30 minutes, then 0.05-0.15 parts of sodium hydroxide and 2-5 parts of 2-ethylhexyl glycidyl ether were added, the temperature was raised to 60-70 ° C and stirred for 5-10 hours, cooled to room temperature, the pH value was adjusted to neutral, and 1-3 times the volume of cold Ether was used to precipitate the product, which was centrifuged and dried to obtain an alkyl-modified cyclodextrin. At 40-50° C. and under a nitrogen atmosphere, 4-6 parts of the alkyl-modified cyclodextrin and 1-3 parts of polycaprolactone-polyethylene glycol were added to 40-60 parts of dimethyl sulfoxide and stirred for 20-40 minutes. Then, 0.4-0.6 parts of dicyclohexylcarbodiimide were added and reacted for 10-15 hours. 1-3 times the volume of cold ether was added to precipitate the product, which was centrifuged and dried to obtain PCL-PEG grafted cyclodextrin.

[0030] 5-15 parts of plant essential oil and 1-3 parts of polylactic acid-glycolic acid copolymer are added to 40-60 parts of ethyl acetate, and the mixture is stirred at 25-35° C. and 400-600 rpm for 15-30 minutes. Then, 5-10 parts of PCL-PEG grafted cyclodextrin are added and stirring is continued for 40-60 minutes to obtain an oil phase. 0.5-2 parts of polyvinyl alcohol are added to 70-150 parts of water, and the mixture is stirred at 25-35° C. and 400-600 rpm for 5-15 minutes to obtain an aqueous phase. The oil phase is added to the aqueous phase, and the mixture is then subjected to a high-pressure homogenizer for 2-5 cycles at a pressure of 40-60 MPa. The ethyl acetate is recovered by rotary evaporation at 45-55° C. and 150-300 mbar, and the mixture is centrifuged and dried to obtain a flavor sustained-release capsule.

[0031] Preferably, the photoinitiator is one or a mixture of two or more of 3-methyl-4-phenylbenzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

[0032] Preferably, the active amine co-initiator is one or a mixture of two or more of p-dimethylaminobenzoic acid isooctyl ester, p-dimethylaminobenzoic acid ethyl ester, N-phenylglycine, N-methyldiethanolamine, and P115 active amine.

[0033] Preferably, the defoamer is any one of defoamer TEGO 830, defoamer TEGO 900, and defoamer TEGO 920.

[0034] Preferably, the solvent is any one of propylene glycol methyl ether, ethyl acetate, butyl acetate, propylene carbonate, and isopropyl alcohol.

[0035] The present invention provides a method for preparing ink with a long-lasting fragrance, comprising the following steps:

[0036] The raw materials are weighed according to the raw material formula, and tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsules, defoaming agent, and solvent are added to a high-speed blender, and stirred at 400-600 rpm for 15-40 minutes to obtain the ink with long-lasting fragrance.

[0037] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0038] 1. The present invention provides an ink with a long-lasting fragrance and a preparation method thereof. The invention comprises: adding silicone acrylate obtained by reacting an alkenyl polysiloxane emulsion with an acrylic acid monomer, an oil phase composed of plant essential oils, polylactic acid-glycolic acid copolymer, PCL-PEG grafted cyclodextrin and ethyl acetate, and an aqueous phase composed of polyvinyl alcohol in water; and subjecting the mixture to high-pressure homogenization, rotary evaporation and drying to produce a fragrance sustained-release capsule. The capsule not only improves the stability, adhesion and curing rate of the ink, but also prolongs the duration of the fragrance of the ink, thereby achieving the purpose of long-lasting fragrance.

[0039] 2. The present invention utilizes a specific organosilicon acrylate that synergizes with polyurethane acrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate to significantly improve the ink's overall properties, including adhesion and gloss. The organosilicon segments form a polysiloxane network through hydrolysis and condensation, imparting low surface energy and excellent flexibility to the material, significantly reducing the interfacial energy difference between the ink and the plastic substrate, thereby enhancing wettability and anchoring. The acrylate monomers form a rigid skeleton with a high cross-linking density through free radical copolymerization. This rigid and flexible interpenetrating network structure not only releases internal stress through deformation of the siloxane chains, preventing cracking, but also forms hydrogen bonds or chemical bonds with the substrate surface through the strong polar groups (ester and hydroxyl groups) of the acrylate, thereby improving adhesion.

[0040] 3. The present invention also incorporates a homemade sustained-release fragrance capsule, which further improves the ink's fragrance stability and prolongs the ink's fragrance compared to directly adding flavoring agents such as plant essential oils. The alkyl-modified cyclodextrin enhances the hydrophobic binding capacity of the β-cyclodextrin cavity, allowing the plant essential oil to be better embedded within the cyclodextrin cavity. The grafting of the polycaprolactone-polyethylene glycol block copolymer introduces amphiphilic interface regulation capabilities. The polycaprolactone segments physically entangle with the cyclodextrin alkyl chains through crystallization, forming a dynamic hydrophobic network, while the polyethylene glycol segments extend in the aqueous phase to form a steric barrier. These dual effects inhibit the outward migration of essential oil molecules. The synergistic effect of microcrack expansion in the PLGA shell and the viscoelastic deformation of PCL, as well as the gradual dissociation of the cyclodextrin cavity, provides long-term sustained release, effectively extending the fragrance release time. DETAILED DESCRIPTION

[0041] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0042] Polyurethane acrylate was purchased from Youming (Shanghai) Chemical Co., Ltd., brand: T20D, viscosity (25°C): 20000-30000 cps.

[0043] The defoaming agent TEGO 830 was purchased from Shanghai Buding Chemical Co., Ltd., brand: German Digo.

[0044] Alkyl polyglycoside APG-0810 was purchased from Hubei Xinjiecheng Chemical Technology Co., Ltd., CAS: 68515-73-1.

[0045] Hydroxypropyl-β-cyclodextrin was purchased from Shandong Runxinda Chemical Co., Ltd., CAS: 128446-35-5.

[0046] Rose essential oil was purchased from Jiangxi Zhonghuan Biotechnology Co., Ltd., CAS: 8007-01-0.

[0047] Polycaprolactone-polyethylene glycol was purchased from Xi'an Qiyue Biotechnology Co., Ltd., model: PCL2000-PEG2000.

[0048] Poly(lactic-co-glycolic acid) copolymer was purchased from Hangzhou Xinqiao Biotechnology Co., Ltd., model: PLGA1000-PEG1000.

[0049] Polyvinyl alcohol was purchased from Shanghai Yuanye Biotechnology Co., Ltd., with a degree of alcoholysis of 98-99% and a viscosity (25° C.) of 25-31 mPa.s.

[0050] Example 1

[0051] This embodiment provides an ink with a long-lasting fragrance, which comprises the following raw materials in parts by weight:

[0052] 40 parts of tripropylene glycol diacrylate, 20 parts of trimethylolpropane triacrylate, 20 parts of polyurethane acrylate, 1 part of silicone acrylate, 4 parts of photoinitiator, 1 part of active amine co-initiator, 3 parts of fragrance sustained-release capsules, 0.3 parts of defoaming agent, and 5 parts of solvent.

[0053] The photoinitiator is 3-methyl-4-phenyl benzophenone; the active amine co-initiator is isooctyl p-dimethylaminobenzoate; the defoamer is defoamer TEGO830; and the solvent is propylene glycol methyl ether.

[0054] The preparation method of the organosilicon acrylate comprises the following steps:

[0055] 2 parts of sodium dodecylbenzenesulfonate, 1 part of alkyl polyglycoside APG-0810, and 12 parts of octamethylcyclotetrasiloxane were added to 85 parts of water by weight, stirred at 35° C. and 200 rpm for 10 minutes, and then circulated for 3 times with a high-pressure homogenizer at a pressure of 50 MPa to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid was adjusted to 3.5, stirred at 72° C. and 200 rpm for 2 hours, and then 3 parts of (methacryloyloxymethyl)methyldiethoxysilane were added and stirred for 6 hours. The mixture was cooled to room temperature and the pH value was adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0056] To 50 parts of alkenyl polysiloxane emulsion, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added in sequence at 85° C. under a nitrogen atmosphere, and the mixture was reacted for 5 hours. The acrylic acid monomer was a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 4:1. The mixture was cooled to room temperature to obtain a polymer emulsion. 3 times the volume of anhydrous ethanol was added to the polymer emulsion, and the mixture was stirred at 500 rpm for 1 hour to break the emulsion. The mixture was centrifuged, and the precipitate was collected and dried to obtain silicone acrylate.

[0057] The preparation method of the flavor sustained-release capsule comprises the following steps:

[0058] By weight, 5 parts of hydroxypropyl-β-cyclodextrin were added to 100 parts of a 60wt% ethanol aqueous solution, stirred at 45°C and 300rpm for 20min, then 0.1 parts of sodium hydroxide and 3.2 parts of 2-ethylhexyl glycidyl ether were added, the temperature was raised to 65°C and stirred for 8h, cooled to room temperature, the pH value was adjusted to neutral, 2 volumes of cold ether were added to precipitate, centrifuged, and dried to obtain an alkyl-modified cyclodextrin; 5 parts of alkyl-modified cyclodextrin and 2 parts of polycaprolactone-polyethylene glycol were added to 50 parts of dimethyl sulfoxide at 45°C and under a nitrogen atmosphere, and stirred for 30min, then 0.5 parts of dicyclohexylcarbodiimide were added to react for 12h, 2 volumes of cold ether were added to precipitate, centrifuged, and dried to obtain PCL-PEG grafted cyclodextrin;

[0059] 10 parts of plant essential oil and 2 parts of polylactic acid-glycolic acid copolymer are added to 50 parts of ethyl acetate, wherein the plant essential oil is rose essential oil, and stirred at 30°C and 500 rpm for 20 minutes. Then, 8 parts of PCL-PEG grafted cyclodextrin are added and stirred for 50 minutes to obtain an oil phase; 1 part of polyvinyl alcohol is added to 100 parts of water, and stirred at 30°C and 500 rpm for 10 minutes to obtain an aqueous phase; the oil phase is added to the aqueous phase, and then circulated for 3 times using a high-pressure homogenizer with a pressure of 50 MPa. The ethyl acetate is recovered by rotary evaporation at 50°C and 200 mbar, centrifuged, and dried to obtain flavor sustained-release capsules.

[0060] This embodiment provides a method for preparing an ink with a long-lasting fragrance, comprising the following steps:

[0061] The raw materials were weighed according to the raw material formula, and tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsules, defoaming agent, and solvent were added to a high-speed blender and stirred at 600 rpm for 15 minutes to obtain the ink with long-lasting fragrance.

[0062] Example 2

[0063] This embodiment provides an ink with a long-lasting fragrance, which comprises the following raw materials in parts by weight:

[0064] 20 parts of tripropylene glycol diacrylate, 10 parts of trimethylolpropane triacrylate, 50 parts of polyurethane acrylate, 5 parts of silicone acrylate, 6 parts of photoinitiator, 5 parts of active amine co-initiator, 5 parts of fragrance sustained-release capsules, 0.5 parts of defoaming agent, and 15 parts of solvent.

[0065] The photoinitiator is 3-methyl-4-phenyl benzophenone; the active amine co-initiator is isooctyl p-dimethylaminobenzoate; the defoamer is defoamer TEGO830; and the solvent is propylene glycol methyl ether.

[0066] The preparation method of the silicone acrylate is the same as that of Example 1; the preparation method of the flavor sustained-release capsule is the same as that of Example 1.

[0067] This embodiment provides a method for preparing an ink with a long-lasting fragrance, comprising the following steps:

[0068] The raw materials were weighed according to the raw material formula, and tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsules, defoaming agent, and solvent were added to a high-speed blender and stirred at 400 rpm for 40 minutes to obtain the ink with long-lasting fragrance.

[0069] Example 3

[0070] This embodiment provides an ink with a long-lasting fragrance, which comprises the following raw materials in parts by weight:

[0071] 30 parts of tripropylene glycol diacrylate, 15 parts of trimethylolpropane triacrylate, 30 parts of polyurethane acrylate, 3 parts of silicone acrylate, 5 parts of photoinitiator, 2 parts of active amine co-initiator, 4 parts of fragrance sustained-release capsules, 6 parts of 0.4 parts of defoaming agent, and 10 parts of solvent.

[0072] The photoinitiator is 3-methyl-4-phenyl benzophenone; the active amine co-initiator is isooctyl p-dimethylaminobenzoate; the defoamer is defoamer TEGO830; and the solvent is propylene glycol methyl ether.

[0073] The preparation method of the silicone acrylate is the same as that of Example 1; the preparation method of the flavor sustained-release capsule is the same as that of Example 1.

[0074] This embodiment provides a method for preparing an ink with a long-lasting fragrance, comprising the following steps:

[0075] The raw materials were weighed according to the raw material formula, and tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsules, defoaming agent, and solvent were added into a high-speed blender and stirred at 450 rpm for 30 minutes to obtain the ink with long-lasting fragrance.

[0076] Comparative Example 1

[0077] The difference between this comparative example and Example 3 is that the preparation method of the silicone acrylate is different, specifically as follows: the preparation method of the silicone acrylate comprises the following steps:

[0078] 2 parts of sodium dodecylbenzenesulfonate, 1 part of alkyl polyglycoside APG-0810, and 12 parts of hexamethylcyclotrisiloxane were added to 85 parts of water by weight, stirred at 35° C. and 200 rpm for 10 minutes, and then circulated for 3 times with a high-pressure homogenizer at a pressure of 50 MPa to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid was adjusted to 3.5, stirred at 72° C. and 200 rpm for 2 hours, and then 3 parts of (methacryloyloxymethyl)methyldiethoxysilane were added and stirred for 6 hours. The mixture was cooled to room temperature and the pH value was adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0079] To 50 parts of alkenyl polysiloxane emulsion, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added in sequence at 85° C. under a nitrogen atmosphere, and the mixture was reacted for 5 hours. The acrylic acid monomer was a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 4:1. The mixture was cooled to room temperature to obtain a polymer emulsion. 3 times the volume of anhydrous ethanol was added to the polymer emulsion, and the mixture was stirred at 500 rpm for 1 hour to break the emulsion. The mixture was centrifuged, and the precipitate was collected and dried to obtain silicone acrylate.

[0080] Comparative Example 2

[0081] The difference between this comparative example and Example 3 is that the preparation method of the silicone acrylate is different, specifically as follows: the preparation method of the silicone acrylate comprises the following steps:

[0082] 2 parts of sodium dodecylbenzenesulfonate, 1 part of alkyl polyglycoside APG-0810, and 12 parts of octamethylcyclotetrasiloxane were added to 85 parts of water by weight, and stirred at 35° C. and 200 rpm for 10 minutes, and then circulated for 3 times with a high-pressure homogenizer at a pressure of 50 MPa to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid was adjusted to 3.5, and stirred at 72° C. and 200 rpm for 2 hours, and then 3 parts of methylvinyldimethoxysilane were added and stirred for 6 hours. The mixture was cooled to room temperature and the pH value was adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0083] To 50 parts of alkenyl polysiloxane emulsion, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added in sequence at 85° C. under a nitrogen atmosphere, and the mixture was reacted for 5 hours. The acrylic acid monomer was a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 4:1. The mixture was cooled to room temperature to obtain a polymer emulsion. 3 times the volume of anhydrous ethanol was added to the polymer emulsion, and the mixture was stirred at 500 rpm for 1 hour to break the emulsion. The mixture was centrifuged, and the precipitate was collected and dried to obtain silicone acrylate.

[0084] Comparative Example 3

[0085] The difference between this comparative example and Example 3 is that the preparation method of the silicone acrylate is different, specifically as follows: the preparation method of the silicone acrylate comprises the following steps:

[0086] 2 parts of sodium dodecylbenzenesulfonate, 1 part of alkyl polyglycoside APG-0810, and 12 parts of octamethylcyclotetrasiloxane were added to 85 parts of water by weight, stirred at 35° C. and 200 rpm for 10 minutes, and then circulated for 3 times with a high-pressure homogenizer at a pressure of 50 MPa to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid was adjusted to 3.5, stirred at 72° C. and 200 rpm for 2 hours, and then 3 parts of (methacryloyloxymethyl)methyldiethoxysilane were added and stirred for 6 hours. The mixture was cooled to room temperature and the pH value was adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0087] To 50 parts of alkenyl polysiloxane emulsion, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added in sequence at 85° C. under a nitrogen atmosphere, and the mixture was reacted for 5 hours. The acrylic acid monomer was neopentyl glycol diacrylate, and the mixture was cooled to room temperature to obtain a polymer emulsion. 3 times the volume of anhydrous ethanol was added to the polymer emulsion, and the mixture was stirred at 500 rpm for 1 hour to break the emulsion. The mixture was centrifuged, and the precipitate was collected and dried to obtain silicone acrylate.

[0088] Comparative Example 4

[0089] The difference between this comparative example and Example 3 is that the preparation method of the silicone acrylate is different, specifically as follows: the preparation method of the silicone acrylate comprises the following steps:

[0090] 2 parts of sodium dodecylbenzenesulfonate, 1 part of alkyl polyglycoside APG-0810, and 12 parts of octamethylcyclotetrasiloxane were added to 85 parts of water by weight, stirred at 35° C. and 200 rpm for 10 minutes, and then circulated for 3 times with a high-pressure homogenizer at a pressure of 50 MPa to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid was adjusted to 3.5, stirred at 72° C. and 200 rpm for 2 hours, and then 3 parts of (methacryloyloxymethyl)methyldiethoxysilane were added and stirred for 6 hours. The mixture was cooled to room temperature and the pH value was adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0091] To 50 parts of alkenyl polysiloxane emulsion, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added in sequence at 85° C. under a nitrogen atmosphere, and the mixture was reacted for 5 hours. The acrylic acid monomer was ethoxylated trimethylolpropane triacrylate, and the mixture was cooled to room temperature to obtain a polymer emulsion. 3 times the volume of anhydrous ethanol was added to the polymer emulsion, and the mixture was stirred at 500 rpm for 1 hour to break the emulsion. The mixture was centrifuged, and the precipitate was collected and dried to obtain silicone acrylate.

[0092] Comparative Example 5

[0093] The difference between this comparative example and Example 3 is that the preparation method of the flavor sustained-release capsule is different, which is as follows: the preparation method of the flavor sustained-release capsule comprises the following steps:

[0094] 5 parts by weight of hydroxypropyl-β-cyclodextrin were added to 100 parts of a 60 wt% aqueous ethanol solution, stirred at 45°C and 300 rpm for 20 minutes, then 0.1 parts of sodium hydroxide and 3.2 parts of 2-ethylhexyl glycidyl ether were added, the temperature was raised to 65°C and stirred for 8 hours, cooled to room temperature, the pH value was adjusted to neutral, 2 volumes of cold ether were added to precipitate, centrifuged, and dried to obtain an alkyl-modified cyclodextrin;

[0095] 10 parts of plant essential oil and 2 parts of polylactic acid-glycolic acid copolymer are added to 50 parts of ethyl acetate, wherein the plant essential oil is rose essential oil, and stirred at 30°C and 500 rpm for 20 minutes. Then, 8 parts of alkyl-modified cyclodextrin are added and stirred for 50 minutes to obtain an oil phase. 1 part of polyvinyl alcohol is added to 100 parts of water, and stirred at 30°C and 500 rpm for 10 minutes to obtain an aqueous phase. The oil phase is added to the aqueous phase, and then cyclically treated three times using a high-pressure homogenizer at a pressure of 50 MPa. The ethyl acetate is recovered by rotary evaporation at 50°C and 200 mbar, centrifuged, and dried to obtain flavor sustained-release capsules.

[0096] Comparative Example 6

[0097] The difference between this comparative example and Example 3 is that the preparation method of the flavor sustained-release capsule is different, which is as follows: the preparation method of the flavor sustained-release capsule comprises the following steps:

[0098] The method comprises the following steps: adding 10 parts of plant essential oil and 2 parts of polylactic acid-glycolic acid copolymer by weight to 50 parts of ethyl acetate, wherein the plant essential oil is rose essential oil, stirring the mixture at 30°C and 500 rpm for 20 minutes, then adding 8 parts of hydroxypropyl-β-cyclodextrin and continuing to stir the mixture for 50 minutes to obtain an oil phase; adding 1 part of polyvinyl alcohol to 100 parts of water, stirring the mixture at 30°C and 500 rpm for 10 minutes to obtain an aqueous phase; adding the oil phase to the aqueous phase, and then cyclically treating the mixture three times using a high-pressure homogenizer at a pressure of 50 MPa, recovering the ethyl acetate by rotary evaporation at 50°C and 200 mbar, centrifuging the mixture, and drying the mixture to obtain a flavor sustained-release capsule.

[0099] Performance Testing

[0100] 1. Determine the basic properties of the long-lasting fragrance inks obtained in Examples 1-3 and Comparative Examples 1-6 of the present invention. Screen printing was performed on a plastic substrate (PET film) with an ink printing amount of 10 g / m 2Among them, glossiness is tested with reference to GB / T13217.2-2009; adhesion is tested with reference to GB / T9286-2021 (0-5 levels, 5 is the worst); and adhesion fastness is tested with reference to GB / T13217.7-2009.

[0101] 2. Determine the loading rate of the plant essential oil in the flavor sustained-release capsules of Example 1 and Comparative Examples 5-6 of the present invention, wherein the loading rate % = (M 香味缓释胶囊 -M 壁材) / M 壁材 ×100%,M 壁材 It is the sum of the masses of poly(lactic acid-co-glycolic acid) and PCL-PEG grafted cyclodextrin.

[0102] 3. Determine the fragrance stability of the long-lasting fragrance inks obtained in Examples 1-3 and Comparative Examples 5-6 in an accelerated aging test. Gravure printing was performed on kraft paper (stiffness 90 g×cm) with an ink printing amount of 10 g / m 2 , and obtain printed samples, which were placed in an ultraviolet aging test chamber (UVA-340nm, 0.7W / m 2 The test conditions were: temperature 40±2°C, relative humidity 75±5%, and the test period was 60 days. The changes in the aroma were recorded. The results are shown in Table 1.

[0103] Table 1: Test results of various properties of ink

[0104]

[0105] It can be seen from the above test results that the long-lasting fragrance inks prepared in Examples 1-3 of the present invention have good gloss, adhesion and fragrance stability, especially the long-lasting fragrance ink described in Example 3 has the best comprehensive performance. This is because the present invention significantly improves the gloss, adhesion and fragrance stability of the ink by adding specific fragrance sustained-release capsules and silicone acrylate to the ink formula. Comparing Examples 1-3 and Comparative Examples 1-4, it can be seen that since Comparative Examples 1-4 do not use silicone acrylate prepared by a specific method, its gloss, adhesion and other test results are significantly worse than those of Examples 1-3; Comparing Examples 1-3 and Comparative Examples 5-6, it can be seen that since Comparative Examples 5-6 do not use fragrance sustained-release capsules prepared by a specific method, its loading rate and fragrance stability are both worse than those of Examples 1-3. Comparison of the test results of the above examples and comparative examples further demonstrates the importance of the technical solution defined in the present invention for its technical effects.

[0106] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A long-lasting fragrance ink, characterized in that: Calculated by weight, it includes the following raw materials: 20-40 parts of tripropylene glycol diacrylate, 10-20 parts of trimethylolpropane triacrylate, 20-50 parts of polyurethane acrylate, 1-5 parts of silicone acrylate, 4-6 parts of photoinitiator, 1-5 parts of active amine co-initiator, 3-5 parts of fragrance sustained-release capsules, 0.3-0.5 parts of defoamer and 5-15 parts of solvent; The preparation method of the organosilicon acrylate comprises: adding alkylbenzene sulfonate, alkyl glucoside, and octamethylcyclotetrasiloxane to water, heating and stirring, and then circulating the mixture with a high-pressure homogenizer to obtain an emulsified intermediate liquid; adjusting the emulsified intermediate liquid to acidity, heating and stirring, then adding (methacryloyloxymethyl)methyldiethoxysilane, continuing to stir, cooling, and adjusting the pH to obtain an alkenyl polysiloxane emulsion; sequentially adding persulfate and acrylic acid monomer to the alkenyl polysiloxane emulsion, heating and reacting, cooling, and obtaining a polymer emulsion; and breaking the emulsion, centrifuging, and drying to obtain the organosilicon acrylate. The preparation method of the flavor sustained-release capsule comprises the following steps: Hydroxypropyl-β-cyclodextrin is added to an ethanol aqueous solution and heated with stirring, and then a base and 2-ethylhexyl glycidyl ether are added and stirred for reaction, cooled, pH adjusted, precipitated, centrifuged, and dried to obtain an alkyl-modified cyclodextrin; the alkyl-modified cyclodextrin and polycaprolactone-polyethylene glycol are added to dimethyl sulfoxide and heated with stirring, and then dicyclohexylcarbodiimide is added for reaction, precipitated, centrifuged, and dried to obtain PCL-PEG grafted cyclodextrin; Plant essential oil and poly(lactic acid-co-glycolic acid) copolymer are added to ethyl acetate and stirred, and then PCL-PEG grafted cyclodextrin is added and stirred continuously to obtain an oil phase; polyvinyl alcohol is added to water and stirred to obtain an aqueous phase; the oil phase is added to the aqueous phase, and then circulated through a high-pressure homogenizer, rotary evaporated, centrifuged, and dried to obtain a flavor sustained-release capsule; The acrylic monomer is a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 3-5:

1.

2. The ink with a long-lasting fragrance according to claim 1, characterized in that The weight ratio of the alkylbenzene sulfonate, alkyl glucoside, octamethylcyclotetrasiloxane and (methacryloyloxymethyl)methyldiethoxysilane is 1-3:0.5-1.5:10-15:2-4; the weight ratio of the alkenyl polysiloxane emulsion, persulfate and acrylic acid monomer is 40-60:0.1-0.3:15-20.

3. The ink with a long-lasting fragrance according to claim 1, characterized in that The weight ratio of the hydroxypropyl-β-cyclodextrin and 2-ethylhexyl glycidyl ether is 4-6:2-5; the weight ratio of the alkyl-modified cyclodextrin and polycaprolactone-polyethylene glycol is 4-6:1-3; the weight ratio of the plant essential oil to polylactic acid-glycolic acid copolymer, PCL-PEG grafted cyclodextrin, and polyvinyl alcohol is 5-15:1-3:5-10:0.5-2.

4. The ink with a long-lasting fragrance according to claim 1, characterized in that The plant essential oil is any one of rose essential oil, lemon essential oil, lavender essential oil, grapefruit essential oil and peony essential oil.

5. The ink with a long-lasting fragrance according to claim 1, characterized in that The photoinitiator is one or a mixture of two or more of 3-methyl-4-phenylbenzophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2-isopropylthioxanthone, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; the active amine co-initiator is one or a mixture of two or more of p-dimethylaminobenzoic acid isooctyl ester, ethyl p-dimethylaminobenzoate, N-phenylglycine, N-methyldiethanolamine, and P115 active amine.

6. The ink with a long-lasting fragrance according to claim 1, characterized in that: The defoamer is any one of defoamer TEGO830, defoamer TEGO 900, and defoamer TEGO 920; the solvent is any one of propylene glycol methyl ether, ethyl acetate, butyl acetate, propylene carbonate, and isopropyl alcohol.

7. The method for preparing a long-lasting fragrance ink according to any one of claims 1 to 6, characterized in that: The following steps are involved: The raw materials are weighed according to the raw material formula, and tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsules, defoaming agent, and solvent are added to a high-speed blender, and stirred at 400-600 rpm for 15-40 minutes to obtain the ink with long-lasting fragrance.

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