Ink with lasting fragrance and preparation method thereof

Abstract

The invention provides printing ink with lasting fragrance and a preparation method thereof, and belongs to the technical field of printing ink. The printing ink with the lasting fragrance is prepared from the following raw materials in parts by weight: 20 to 40 parts of tripropylene glycol diacrylate, 10 to 20 parts of trimethylolpropane triacrylate, 20 to 50 parts of polyurethane acrylate, 1 to 5 parts of organosilicone acrylate, 4 to 6 parts of a photoinitiator, 1 to 5 parts of an active amine co-initiator, 3 to 5 parts of fragrance sustained-release capsules, 0.3 to 0.5 part of a de-foaming agent and 5 to 15 parts of a solvent. Wherein the fragrance sustained-release capsule is prepared from an oil phase and a water phase through high-pressure homogenization, rotary evaporation and drying, the oil phase is prepared from plant essential oil, a polylactic acid-glycolic acid copolymer, PCL-PEG grafted cyclodextrin and ethyl acetate, and the water phase is prepared from polyvinyl alcohol and water. The ink prepared by the invention has the characteristics of long lasting time of fragrance, good stability, strong adhesive force, fast curing, scratch resistance, greenness, environmental protection and the like.

Description

Technical Field

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

[0002] As the packaging industry continues to increase its demand for anti-counterfeiting functions and sensory experience, anti-counterfeiting inks are increasingly used in the printing field. Although traditional anti-counterfeiting methods such as laser holography and QR codes can achieve visual anti-counterfeiting effects, they often have limitations such as being easily copied or requiring special equipment for identification. In contrast, anti-counterfeiting inks directly integrate anti-counterfeiting functions into the printing process by utilizing the special properties of the material itself, such as optical color change, temperature-sensitive response, and odor marking, so that they are both concealed and intuitive, and are particularly suitable for the packaging of high-value-added products such as tobacco and medicines. Specifically, the core function of anti-counterfeiting inks is to achieve authenticity identification through differences in physical or chemical properties. For example, microcapsule scented inks can encapsulate essential oils in polymer materials, release odors through friction or pressure, and form a unique "olfactory anti-counterfeiting" mark. This approach not only improves the technical level of anti-counterfeiting, but also enhances interactivity by enhancing consumers' 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 relatively high, and in actual applications, the recognition accuracy may be affected by the instability of external force; second, the use of thermochromic or thermoluminescent materials changes 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; third, the anti-counterfeiting function is achieved through electrochromic or electroluminescent materials, 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; fourth, relying on photochromic, fluorescent or laser holographic 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 characteristics 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 ink, it can be improved by optimizing material formula, improving preparation process and introducing new functional materials. In terms of material formula, the fragrance release time can be prolonged by enhancing the stability of polymer carrier, while improving the scratch resistance and printing feel of ink; in the preparation process, more sophisticated microcapsule encapsulation technology can be used to effectively reduce the volatilization loss of essential oils during storage and transportation, thereby improving the durability of fragrance; combined with nanotechnology, functional particles are evenly dispersed in the ink system, thereby further improving its comprehensive performance. However, the above method still has some disadvantages. For example, the aging characteristics of polymer materials will cause the fragrance to be significantly weakened over time, the durability is poor, and the adhesion is reduced and easy to deink when solidified on non-absorbent materials such as metal films and plastics. 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 and 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 the fragrance of the ink for a long time, but also has the characteristics of good stability, strong adhesion, fast curing, etc.

[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 flavor sustained-release capsules, 0.3-0.5 parts of defoaming agent, and 5-15 parts of solvent.

[0009] Preferably, the method for preparing the organosilicon acrylate comprises the following steps:

[0010] Alkylbenzene sulfonate (e.g. sodium dodecylbenzene sulfonate), alkyl glucoside (e.g. APG-0810), and octamethylcyclotetrasiloxane are added to water, heated and stirred, and then circulated with 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] To the alkenyl polysiloxane emulsion, persulfate (such as ammonium persulfate) and acrylic acid monomer are sequentially added, heated for reaction, and cooled to obtain a polymer emulsion; anhydrous ethanol is added to the polymer emulsion to break the emulsion, centrifuged, the precipitate is collected, and dried to obtain silicone acrylate.

[0012] The present invention adds the above-mentioned organosilicon acrylate to the ink formula, which can synergize with polyurethane acrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate to significantly improve the comprehensive properties of the ink, such as adhesion fastness and glossiness. The mechanism of action is essentially derived from the synergistic effect of the dual characteristics of its molecular structure and the interface behavior.

[0013] In the preparation process of the organosilicon acrylate of the present invention, firstly, the organosilicon segments using octamethylcyclotetrasiloxane and (methacryloyloxymethyl)methyldiethoxysilane as precursors are hydrolyzed and condensed to form a polysiloxane network, which gives the material low surface energy and excellent flexibility. This characteristic drives the molecules to migrate to the coating surface during the ink curing process to form 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 generates a rigid skeleton with high cross-linking density through free radical copolymerization. This rigid and flexible interpenetrating network structure can release internal stress through the deformation of the siloxane chain to avoid cracking, and can 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 chains tend to form micron-scale domain structures during the phase separation process, and the difference in their 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; 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] In parts by weight, 1-3 parts of sodium dodecylbenzene sulfonate, 0.5-1.5 parts of alkyl polyglycoside APG-0810, and 10-15 parts of octamethylcyclotetrasiloxane are added to 80-100 parts of water, stirred at 30-40° C. and 150-300 rpm for 5-15 minutes, and then circulated for 3-5 times with a high-pressure homogenizer, the pressure of the high-pressure homogenizer is 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 stirred for 5-8 hours, cooled to room temperature, and the pH value is adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0019] At 80-90° C. and in a nitrogen atmosphere, 0.1-0.3 parts of ammonium persulfate and 15-20 parts of acrylic acid monomer are sequentially added to 40-60 parts of alkenyl polysiloxane emulsion, 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, and the mixture is centrifuged, the precipitate is collected, and dried to obtain silicone acrylate.

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

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

[0022] The 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 with a high-pressure homogenizer, ethyl acetate is recovered by rotary evaporation, centrifuged, and dried to obtain a flavor sustained-release capsule.

[0023] In addition, the present invention further improves the fragrance stability of the ink by using the above-mentioned self-made fragrance sustained-release capsule instead of directly adding flavoring agents such as plant essential oils, so that the fragrance of the ink lasts for a long time. First, the alkyl-modified cyclodextrin is grafted with a hydrophobic C8-C10 long chain through the ring-opening reaction of the epoxy group of 2-ethylhexyl glycidyl ether, which significantly enhances the hydrophobic binding ability of the β-cyclodextrin cavity, so that the plant essential oil can be better embedded in the cyclodextrin cavity through van der Waals force and hydrophobic interaction to form 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 chain segments stretch in the aqueous phase to form a steric hindrance layer. 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, forming 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 through the breaking of ester bonds. High-pressure homogenization controls the particle size of oil phase droplets in the nanometer range, and uses interfacial tension to make the composite film evenly cover the surface of the droplets to form 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 stimulation such as friction or temperature, the microcrack expansion of the PLGA shell and the synergistic effect of the viscoelastic deformation of PCL and the gradual dissociation of the cyclodextrin cavity provide long-term sustained release, effectively prolonging 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 are added to 80-120 parts of 50-65wt% ethanol aqueous solution, stirred at 40-50°C and 200-400rpm for 10-30min, then 0.05-0.15 parts of sodium hydroxide and 2-5 parts of 2-ethylhexyl glycidyl ether are added, the temperature is raised to 60-70°C and stirred for 5-10h, cooled to room temperature, the pH value is adjusted to neutral, and 1-3 times the volume of cold Ether is used to precipitate, centrifuge, and dry to obtain alkyl-modified cyclodextrin; at 40-50° C. and in a nitrogen atmosphere, 4-6 parts of alkyl-modified cyclodextrin and 1-3 parts of polycaprolactone-polyethylene glycol are added to 40-60 parts of dimethyl sulfoxide and stirred for 20-40 minutes, and then 0.4-0.6 parts of dicyclohexylcarbodiimide are added to react for 10-15 hours, and 1-3 times the volume of cold ether is added to precipitate, centrifuge, and dry 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, stirred at 25-35°C and 400-600rpm for 15-30min, then 5-10 parts of PCL-PEG grafted cyclodextrin are added and stirred for 40-60min to obtain an oil phase; 0.5-2 parts of polyvinyl alcohol are added to 70-150 parts of water, stirred at 25-35°C and 400-600rpm for 5-15min to obtain an aqueous phase; the oil phase is added to the aqueous phase, and then cyclically treated with a high-pressure homogenizer for 2-5 times, the pressure of the high-pressure homogenizer is 40-60MPa, and ethyl acetate is recovered by rotary evaporation at 45-55°C and 150-300mbar, 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-hydroxycyclohexylphenylketone, 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 lasting fragrance, comprising the following steps:

[0036] Weigh the raw materials according to the raw material formula, add tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsule, defoamer and solvent into a high-speed mixer, stir 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 ink is prepared by adding silicone acrylate obtained by reacting alkenyl polysiloxane emulsion with acrylic acid monomer, and an oil phase composed of plant essential oil, polylactic acid-glycolic acid copolymer, PCL-PEG grafted cyclodextrin and ethyl acetate, and an aqueous phase composed of polyvinyl alcohol in water, and then subjected to high-pressure homogenization, rotary evaporation and drying to prepare a fragrance sustained-release capsule. The ink has not only improved stability, strong adhesion and curing rate, but also prolonged the duration of the fragrance of the ink, thereby achieving the purpose of long-lasting fragrance.

[0039] 2. The present invention adopts a specific organosilicon acrylate, which can work synergistically with polyurethane acrylate, tripropylene glycol diacrylate, and trimethylolpropane triacrylate to significantly improve the comprehensive properties of ink such as adhesion fastness and glossiness. Among them, the organosilicon segment forms a polysiloxane network through hydrolysis and condensation, which gives the material low surface energy and excellent flexibility, significantly reduces the difference in interfacial energy between the ink and the plastic substrate, thereby enhancing wettability and anchoring effect; the acrylate monomer generates a rigid skeleton with high cross-linking density through free radical copolymerization. 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.

[0040] 3. The present invention also adds a homemade flavor sustained-release capsule, which further improves the flavor stability of the ink compared to directly adding flavoring agents such as plant essential oils, making the ink's flavor last longer. Among them, the alkyl-modified cyclodextrin enhances the hydrophobic binding ability of the β-cyclodextrin cavity, so that the plant essential oil can be better embedded in the cyclodextrin cavity; the grafting of polycaprolactone-polyethylene glycol block copolymer introduces amphiphilic interface regulation ability, and the polycaprolactone segment is physically entangled with the alkyl chain of cyclodextrin through crystallization drive to form a dynamic hydrophobic network, while the polyethylene glycol segment stretches in the water phase to form a steric hindrance layer, and the dual effect inhibits the outward migration of essential oil molecules; the microcrack expansion of the PLGA shell layer and the synergistic effect of 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. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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 acid-co-glycolic acid) was purchased from Hangzhou Xinqiao Biotechnology Co., Ltd., model: PLGA1000-PEG1000.

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

[0050] Example 1

[0051] This embodiment provides an ink with a long-lasting fragrance, which includes 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-phenylbenzophenone; 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] In parts by weight, 2 parts of sodium dodecylbenzene sulfonate, 1 part of alkyl polyglycoside APG-0810, and 12 parts of octamethylcyclotetrasiloxane are added to 85 parts of water, stirred at 35° C. and 200 rpm for 10 minutes, and then circulated for 3 times with a high-pressure homogenizer, the pressure of the high-pressure homogenizer is 50 MPa, to obtain an emulsified intermediate liquid; the pH value of the emulsified intermediate liquid is adjusted to 3.5, stirred at 72° C. and 200 rpm for 2 hours, and then 3 parts of (methacryloyloxymethyl)methyldiethoxysilane are added and stirred for 6 hours, cooled to room temperature, and the pH value is adjusted to neutral to obtain an alkenyl polysiloxane emulsion;

[0056] At 85° C. and in a nitrogen atmosphere, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were sequentially added to 50 parts of alkenyl polysiloxane emulsion for reaction for 5 hours, wherein the acrylic acid monomer was a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 4:1, 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 demulsification for 1 hour, centrifuged, 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 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 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 nitrogen atmosphere, 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 500rpm 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 500rpm for 10 minutes to obtain an aqueous phase; the oil phase is added to the aqueous phase, and then cyclically treated 3 times with a high-pressure homogenizer, the pressure of the high-pressure homogenizer is 50MPa, and ethyl acetate is recovered by rotary evaporation at 50°C and 200mbar, centrifuged, and dried to obtain a flavor sustained-release capsule.

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

[0061] Weigh the raw materials according to the raw material formula, add tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsule, defoamer and solvent into a high-speed mixer, and stir 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 includes 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 defoamer, and 15 parts of solvent.

[0065] The photoinitiator is 3-methyl-4-phenylbenzophenone; 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] Weigh the raw materials according to the raw material formula, add tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsule, defoamer and solvent into a high-speed mixer, stir 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 includes 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 0.4 parts of defoamer, and 10 parts of solvent.

[0072] The photoinitiator is 3-methyl-4-phenylbenzophenone; 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] Weigh the raw materials according to the raw material formula, add tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsule, defoamer and solvent into a high-speed mixer, and stir 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, which is as follows: the preparation method of the silicone acrylate comprises the following steps:

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

[0079] At 85° C. and in a nitrogen atmosphere, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were sequentially added to 50 parts of alkenyl polysiloxane emulsion for reaction for 5 hours, wherein the acrylic acid monomer was a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 4:1, 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 demulsification for 1 hour, centrifuged, 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, which is as follows: the preparation method of the silicone acrylate comprises the following steps:

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

[0083] At 85° C. and in a nitrogen atmosphere, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were sequentially added to 50 parts of alkenyl polysiloxane emulsion for reaction for 5 hours, wherein the acrylic acid monomer was a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 4:1, 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 demulsification for 1 hour, centrifuged, 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, which is as follows: the preparation method of the silicone acrylate comprises the following steps:

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

[0087] At 85°C and in a nitrogen atmosphere, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added to 50 parts of alkenyl polysiloxane emulsion in sequence for reaction for 5 hours, wherein the acrylic acid monomer was neopentyl glycol diacrylate, and the mixture was cooled to room temperature to obtain a polymer emulsion. Three 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, the precipitate was collected, and the mixture was 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, which is as follows: the preparation method of the silicone acrylate comprises the following steps:

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

[0091] At 85°C and in a nitrogen atmosphere, 0.15 parts of ammonium persulfate and 18 parts of acrylic acid monomer were added to 50 parts of alkenyl polysiloxane emulsion in sequence for reaction for 5 hours, wherein 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, and the mixture was centrifuged, the precipitate was collected, and the mixture was 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] By weight, 5 parts of hydroxypropyl-β-cyclodextrin are added to 100 parts of 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 are added, the temperature is raised to 65°C and stirred for reaction for 8h, cooled to room temperature, the pH value is adjusted to neutral, 2 times the volume of cold ether is added to precipitate, centrifuged, and dried to obtain 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 500rpm 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 500rpm for 10 minutes to obtain an aqueous phase; the oil phase is added to the aqueous phase, and then cyclically treated 3 times with a high-pressure homogenizer, the pressure of the high-pressure homogenizer is 50MPa, and ethyl acetate is recovered by rotary evaporation at 50°C and 200mbar, centrifuged, and dried to obtain a flavor sustained-release capsule.

[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] By weight, 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 the mixture is stirred at 30°C and 500 rpm for 20 minutes. Then, 8 parts of hydroxypropyl-β-cyclodextrin are added and the mixture is stirred for 50 minutes to obtain an oil phase. 1 part of polyvinyl alcohol is added to 100 parts of water, and the mixture is 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 the mixture is cyclically treated for 3 times by a high-pressure homogenizer, the pressure of the high-pressure homogenizer is 50 MPa, and the ethyl acetate is recovered by rotary evaporation at 50°C and 200 mbar, and the mixture is centrifuged and dried to obtain a flavor sustained-release capsule.

[0099] Performance Testing

[0100] 1. Determine the basic properties of the inks with long-lasting fragrance 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, the glossiness is tested with reference to GB / T13217.2-2009; the adhesion is tested with reference to GB / T9286-2021 (0-5 levels, 5 is the worst); and the adhesion fastness is tested with reference to GB / T13217.7-2009.

[0101] 2. Determine the loading rate of the essential oil in the flavor sustained-release capsules described in 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 stability of the fragrance of the inks obtained in Examples 1-3 and Comparative Examples 5-6 in the accelerated aging test. Gravure printing was performed on kraft paper (stiffness 90 g×cm), and the ink printing amount was 10 g / m 2 The printed samples 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%, test period 60 days, and the aroma changes 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 ink with long-lasting fragrance prepared in Examples 1-3 of the present invention has good gloss, adhesion and fragrance stability, especially the ink with long-lasting fragrance described in Example 3 has the best comprehensive performance, because the present invention significantly improves the gloss, adhesion and fragrance stability of the ink by adding specific fragrance sustained-release capsules and silicone acrylates 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 acrylates prepared by a specific method, the test results of gloss, adhesion, etc. 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, their loading rate and fragrance stability are both worse than those of Examples 1-3. Comparison of the test results of the above embodiments and the comparative examples further proves the importance of the technical scheme defined in the present invention for its technical effect.

[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 the scope of protection of the present invention.

Claims

1. A long-lasting fragrance ink, characterized in that: 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 flavor sustained-release capsules, 0.3-0.5 parts of defoamer and 5-15 parts of solvent.

2. The ink having a long-lasting fragrance according to claim 1, characterized in that: The preparation method of the organosilicon acrylate comprises the following steps: Alkylbenzene sulfonate, alkyl glucoside and octamethylcyclotetrasiloxane are added into water, heated and stirred, and then circulated through a high-pressure homogenizer to obtain an emulsified intermediate liquid; the emulsified intermediate liquid is adjusted to acidity and then heated and stirred, and then (methacryloyloxymethyl)methyldiethoxysilane is added and continued to be stirred, cooled, and pH is adjusted to obtain an alkenyl polysiloxane emulsion; persulfate and acrylic acid monomer are sequentially added into the alkenyl polysiloxane emulsion, heated for reaction, cooled, and obtained a polymer emulsion; demulsification, centrifugation, and drying are performed to obtain silicone acrylate.

3. The ink having a long-lasting fragrance according to claim 1, characterized in that: 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 and stirred, then a base and 2-ethylhexyl glycidyl ether are added and stirred to react, cooled, pH adjusted, precipitated, centrifuged, and dried to obtain an alkyl-modified cyclodextrin; alkyl-modified cyclodextrin and polycaprolactone-polyethylene glycol are added to dimethyl sulfoxide and heated and stirred, then dicyclohexylcarbodiimide is added to react, precipitated, centrifuged, and dried to obtain PCL-PEG grafted cyclodextrin; Add plant essential oil and polylactic acid-glycolic acid copolymer into ethyl acetate and stir, then add PCL-PEG grafted cyclodextrin and continue stirring to obtain an oil phase; add polyvinyl alcohol into water and stir to obtain an aqueous phase; add the oil phase into the aqueous phase, then use a high-pressure homogenizer for circulation treatment, rotary evaporation, centrifugation, and drying to obtain a flavor sustained-release capsule.

4. The ink having a long-lasting fragrance according to claim 2, 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.

5. The ink having a long-lasting fragrance according to claim 2, characterized in that: The acrylic monomer is a mixture of neopentyl glycol diacrylate and ethoxylated trimethylolpropane triacrylate in a weight ratio of 3-5:

1.

6. The ink with a long-lasting fragrance according to claim 3, 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.

7. The ink having a long-lasting fragrance according to claim 3, 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.

8. 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-phenylacetone, 1-hydroxycyclohexyl phenyl 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.

9. 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.

10. The method for preparing the ink with a lasting fragrance according to any one of claims 1 to 9, characterized in that: The following steps are involved: Weigh the raw materials according to the raw material formula, add tripropylene glycol diacrylate, trimethylolpropane triacrylate, polyurethane acrylate, silicone acrylate, photoinitiator, active amine co-initiator, fragrance sustained-release capsule, defoamer and solvent into a high-speed mixer, stir at 400-600 rpm for 15-40 minutes to obtain the ink with long-lasting fragrance.

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