Coated water-based blasting beads and methods of making same

Abstract

The application discloses a coated water-based explosion bead and a preparation method thereof. The coated water-based explosion bead is prepared by the following steps: cross-linking a film structure after sodium ions and calcium ions are exchanged, forming a water-based explosion bead, and then putting the water-based explosion bead into a prepolymer solution of a polymer, so that a dense coating is formed on the outside of the water-based explosion bead, thereby obtaining the coated water-based explosion bead. The coated water-based explosion bead and the preparation method provided by the application not only greatly increase the loading capacity of the essence, but also play a role in long-term locking of the moisture of the core material and increase of the strength of the explosion bead.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of flavor release, and particularly relates to a coated water-based burst bead and a preparation method. BACKGROUND

[0002] The flavoring technology is widely used in people's daily life. The pleasant aroma can make people feel happy, and flavoring is also one of the most important technologies in the process of cigarette production. The existing cigarette flavoring methods mainly include tow flavoring, cigarette paper flavoring, and burst bead flavoring. The tow flavoring and the cigarette paper flavoring are easily affected by factors such as season and storage conditions, and the stability of the flavoring components is poor, and there is a problem of volatile loss of the flavoring. The burst bead flavoring is a new type of flavoring method developed after the cigarette paper flavoring and the tow flavoring. With the increasing diversification of modern life, the demand of consumers for cigarette taste is also increasingly rich, and the burst bead flavoring method is more and more loved by consumers. In recent years, under the demand of the market, the burst bead cigarette has entered a rapid growth stage, and has become a current hotspot, and has a very good development prospect.

[0003] The cigarette burst bead refers to a flavor-loaded capsule embedded in the filter of a cigarette. The structure of the burst bead mainly comprises a core material and a wall material. The core material is various flavors such as lemon flavor, coffee flavor, blueberry flavor, etc. The wall material refers to an elastic and strong shell for closing the core material. Commonly used wall materials at present include gelatin, gum arabic, beeswax, malt dextrin, chitosan, etc. Compared with the traditional flavoring method, the burst bead adopts a non-combustion flavoring method, and the flavor is wrapped in the wall material, which can effectively prevent the loss of the flavor. Consumers can selectively break it when smoking to release the internal flavor, enrich the taste of the cigarette, and also increase the humidity of the smoke.

[0004] The burst bead can be divided into a water-in-oil system and an oil-in-water system according to the different wrapped core materials. The water-in-oil system is used to wrap water-soluble flavors, and the water phase is the internal phase and the oil is the external phase. The oil-in-water system is opposite to the water-in-oil system. The oil-in-water system uses oil-soluble flavors as the core material, and some organic solvents are introduced in the preparation process, which need a series of subsequent treatment processes to remove them, adding cost and difficulty to the production process. The cigarette burst beads on the market at present mainly wrap oil-soluble flavors. Under the current technology, the preparation process of most burst beads cannot wrap water-soluble flavors, greatly reducing the range of available flavors for the core material of the burst bead. The earliest burst bead wall material is gelatin, but its poor high-temperature resistance has greatly limited its use. When other materials are used as the wall material, there are various defects, such as poor toughness of beeswax, poor film-forming ability of malt dextrin, and low viscosity of high-concentration malt dextrin, and poor solubility of chitosan.

[0005] Compared with oil-soluble essence, water-soluble essence has more types, can dissolve part of harmful components such as hydrogen cyanide in smoke, has no irritation and is more suitable for being used as the core material of the explosion bead. Most of the water-in-oil explosion beads developed at present have the defects of complex production process, no breaking feeling, easy to break and the like, which greatly reduce the practicability. Therefore, it is of great significance to develop the explosion bead capable of wrapping water-soluble essence and having practicability.

[0006] In the preparation process of the existing water-in-oil system explosion bead for cigarettes, there are many problems, such as: the water-soluble flavor is wrapped by three or even four layers of structure, the production process is complex, the cost is high, and the product strength is not enough. The film structure formed by photo-crosslinking of the resin (such as bisphenol A epoxy acrylate resin) is not easy to process and form in the later stage, and the crosslinking agent used has toxicity. In addition, the production equipment in the existing production process is also relatively complex, and multiple liquid storage tanks and coaxial double-layer drop heads are often used in combination, and a large amount of cooling liquid is also needed, which has high requirements for the production equipment, the production process is relatively complex, and the yield is low.

[0007] Invention purposes

[0008] Based on the deficiencies of the prior art, the present application provides a coated water-based explosion bead capable of wrapping water-soluble core material and a preparation method, which can be used in tobacco products.

[0009] To achieve the purpose of the present application, the following technical solutions are adopted:

[0010] The present application discloses a preparation method of a coated water-based explosion bead, which is method one or method two.

[0011] Method one: sodium alginate, sodium carboxylate and water-soluble essence are fully mixed in deionized water, and then dropped into a saturated calcium salt aqueous solution to obtain a water-based explosion bead (the explosion bead is replaced by sodium ions and calcium ions to form a dense shell); the water-based explosion bead is added to a prepolymer solution, and further polymerization and curing are initiated by heating to form a coating on the outside of the water-based explosion bead, so as to achieve better encapsulation of the essence, and obtain a coated water-based explosion bead.

[0012] Method two: water-soluble essence is used as a solvent to configure a saturated calcium salt essence solution, which is dropped into a mixed aqueous solution of sodium alginate and sodium carboxylate to obtain a water-based explosion bead (the explosion bead is replaced by sodium ions and calcium ions to form a dense shell); then the water-based explosion bead is immersed in a saturated calcium salt aqueous solution to form two layers of encapsulation on the surface of the water-based explosion bead; the encapsulated water-based explosion bead is added to a prepolymer solution, and further polymerization and curing are initiated by heating to form a coating on the outside of the water-based explosion bead, so as to achieve better encapsulation of the essence, and obtain a coated water-based explosion bead.

[0013] The above-mentioned method one specifically includes the following steps:

[0014] (1)Mixing water-soluble essence, sodium alginate and sodium carboxylate in deionized water and stirring to form a homogeneous solution; in the homogeneous solution, the ratio of sodium alginate to deionized water is 1-5 g: 100 mL, the mass ratio of sodium alginate to sodium carboxylate is 1:0.3-1.5, and the volume ratio of water-soluble essence to deionized water is 0.1-0.5:1.

[0015] (2) Continuously adding calcium salt into a beaker containing deionized water, stirring while ultrasonicating, until a small amount of calcium salt precipitates at the bottom of the beaker and does not dissolve any more. Filtering the excess precipitate at the bottom to obtain a saturated calcium salt aqueous solution.

[0016] (3) Weighing monomers and initiators into a conical flask, ultrasonicating to dissolve the initiator. Placing the conical flask in a water bath at a certain temperature for a certain period of time, placing the conical flask in cold water to cool to room temperature to terminate the reaction, and preparing a prepolymer solution.

[0017] (4) Stirring the saturated calcium salt aqueous solution (preferably, the stirring speed is 50-300 rpm), while dropping the homogeneous solution into it to obtain water-based blasting beads, continuing to soak for 10-45 s, then filtering, rinsing with deionized water to remove the residual calcium salt solution on the outer surface, and after rinsing is completed, absorbing the deionized water on the surface of the water-based blasting beads with filter paper, and drying at room temperature.

[0018] (5) Placing the surface-dried water-based blasting beads into the prepolymer solution for 15-45 s, then taking them out, placing them on tin paper, and placing them in an oven for drying (40-60°C for 1-5 min) to solidify the prepolymer on the surface of the water-based blasting beads and form a thin film.

[0019] (6) Repeating step (5) 2-4 times to obtain coated water-based blasting beads.

[0020] The above method two specifically includes the following steps:

[0021] (1) Continuously adding calcium salt into water-soluble essence, stirring with a glass rod while ultrasonicating, until a small amount of calcium salt precipitates at the bottom of the beaker and does not dissolve any more; filtering the excess precipitate at the bottom to obtain a saturated calcium salt essence solution. Continuously adding calcium salt into a beaker containing deionized water, stirring while ultrasonicating, until a small amount of calcium salt precipitates at the bottom of the beaker and does not dissolve any more. Filtering the excess precipitate at the bottom to obtain a saturated calcium salt aqueous solution.

[0022] (2) Mixing sodium alginate and sodium carboxylate in deionized water and stirring to form a homogeneous solution. In the homogeneous solution, the ratio of sodium alginate to deionized water is 0.3-2 g: 100 mL, and the mass ratio of sodium alginate to sodium carboxylate is 1:0.5-2.

[0023] (3) Weigh monomer and initiator in a conical flask, and dissolve the initiator by ultrasonic. Put the conical flask in a water bath at a certain temperature for a certain time, stop heating, and put the conical flask in cold water to cool to room temperature to terminate the reaction, and prepare a prepolymer solution.

[0024] (4) Drop the saturated calcium salt flavor solution into the homogeneous solution to form an aqueous explosion bead, take it out after 20-60 s of continuous soaking, and immediately put it into a saturated calcium salt aqueous solution stirred at a speed of 100-400 rpm for 1-5 min to form two layers of encapsulation on the surface of the aqueous explosion bead.

[0025] (5) Put the encapsulated aqueous explosion bead into the prepolymer solution for 30-60 s of soaking, take it out, put it on a tin paper, and put it into an oven for drying (45-75℃ for 1-5 min) to solidify the prepolymer on the surface of the aqueous explosion bead and form a thin film.

[0026] (6) Repeat step (5) 2-4 times to obtain a coated aqueous explosion bead.

[0027] Preferably, the sodium carboxylate is one or more of sodium carboxymethyl cellulose, sodium polyacrylate, sodium polymethacrylate, and sodium ethylenediaminetetraacetate.

[0028] Preferably, the water-soluble flavor used is a mixed fruit flavor, a lemon flavor, a coffee flavor, or a blueberry flavor, etc.

[0029] Preferably, the calcium salt is one or more of calcium chloride, calcium acetate, and calcium lactate.

[0030] Preferably, the monomer of the prepolymer solution is methyl methacrylate, acrylate methyl ester, styrene, or methyl styrene, the initiator is azobisisobutyronitrile or dibenzoyl peroxide, the temperature of water bath heating is 70-90℃, and the time is 15-30 min.

[0031] Compared with the prior art, the beneficial effects of the present application are embodied in:

[0032] 1. The present application mixes sodium alginate with other sodium carboxylates to solve the problem of insufficient brittleness and difficulty in breaking due to the excessively high elasticity of the outer wall of the sodium alginate explosion bead.

[0033] 2. The present application encapsulates polymers such as polymethyl methacrylate, polystyrene, and polymethacrylate on the outside of the explosion bead. On the one hand, it can prevent the leakage of the flavor in the explosion bead after long-term storage, and at the same time, it can impart brittleness to the explosion bead to make it emit a crisp sound when crushed. On the other hand, the above polymers are low in cost and can be prepared by one-step bulk polymerization, greatly saving production costs.

[0034] 3. The method in Method 2 prepared a saturated calcium salt fragrance solution using water-soluble fragrance as a solvent, and then added it dropwise into a mixed aqueous solution of sodium alginate and sodium carboxylate, so that the fragrance content in the inner encapsulation core material reached nearly 100%, which significantly improved the fragrance carrying capacity.

[0035] 4. The preparation process of this invention uses a pure water system, overcoming the shortcomings of traditional oil-in-water systems and expanding the range of fragrances that can be used in the core material. Furthermore, it does not use any organic solvents, other surfactants, coagulants, or crosslinking agents, offering advantages such as safety, convenience, biocompatibility, and low pollution.

[0036] 5. Compared with other systems that encapsulate water-soluble core materials, this invention overcomes the disadvantages of complex production processes, lack of burstability, and fragility, resulting in novel coated water-based burst beads that are adjustable in size, regular in shape, produce a cracking sound when popped, and are stable over a long period. Furthermore, the core material content can be adjusted according to requirements, ensuring a sufficiently rich aroma when the beads are popped. The manufacturing process of this invention is relatively simple, simplifying production equipment, and it features low energy consumption, high yield, and significantly reduced production costs.

[0037] 6. This invention employs two different approaches and methods, both involving cross-linking through an ion exchange reaction between sodium and calcium ions in sodium carboxylate, forming an irreversible, dense film structure on the surface to create water-based burst beads that encapsulate the core material. However, after prolonged storage, the core material is prone to leakage. This invention uses a polymer prepolymer solution as the outer coating of the burst beads. On one hand, this enhances the water-locking function, preventing the core material from leaking out and allowing the water-based burst beads to maintain their shape for a longer period. On the other hand, the polymer shell formed on the outermost layer of the water-based burst beads is relatively hard, enhancing its mechanical strength and producing a crisp sound when the beads are crushed, providing a pleasant bursting experience.

[0038] 7. The above-described method for preparing popping beads can also be used to encapsulate other core materials. On one hand, it can encapsulate drugs for disease treatment, preventing unnecessary loss during circulation after the drug enters the body. For example, encapsulating curcumin imparts antioxidant and anti-inflammatory effects, and encapsulating lactic acid bacteria can treat intestinal diseases, releasing the drug through water absorption, swelling, and rupture within the body. On the other hand, it can also serve as an adsorbent for heavy metal ions, adsorbing Pb, Hg, Ni, Cr, etc., in industrial wastewater. Furthermore, it can be used to encapsulate fruit juice and edible pulp for making popping beads in milk tea, and can also encapsulate fluorescent substances and dye molecules, demonstrating its wide range of applications. Attached Figure Description

[0039] Figure 1 This is a schematic diagram of the production process of coated water-based burst beads in Embodiment 1 of the present invention.

[0040] Figure 2 The production process diagram of the coated water-based burst beads in the embodiment 2 of the present application.

[0041] Figure 3 The finished product display diagram of the coated water-based burst beads prepared in the embodiment 1 of the present application.

[0042] Figure 4 The finished product display diagram of the coated water-based burst beads prepared in the embodiment 2 of the present application.

[0043] Figure 5 The infrared spectrograms of the sodium alginate before and after cross-linking with calcium ions.

[0044] Figure 6 The stability test of the water-based burst beads prepared in the embodiment 1 of the present application before and after coating.

[0045] Figure 7 The stability test of the water-based burst beads prepared in the embodiment 2 of the present application before and after coating.

[0046] Figure 8 The partial EDS energy spectrum analysis of the burst beads in the embodiment 2 of the present application, wherein: a diagram is a partial cross-section image, b diagram is an element analysis image of sodium element, and c diagram is an element analysis image of calcium element. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical scheme and advantages of the embodiments of the present application more clear, the technical scheme in the embodiments of the present application is described clearly and completely. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0048] Embodiment 1

[0049] The embodiment provides a coated water-based burst bead, and the preparation steps are as follows:

[0050] (1) 2 mL of tobacco thermal reaction flavor, 0.16 g of sodium alginate and 0.11 g of sodium carboxymethyl cellulose are mixed and placed in 8 mL of deionized water, and a homogeneous solution is formed by fully stirring at a rotation speed of 450 rpm.

[0051] (2) Calcium acetate is continuously added to a beaker containing deionized water, and the beaker is stirred with a glass rod under ultrasonic condition until a small amount of calcium salt precipitate is not dissolved at the bottom of the beaker. The excess precipitate at the bottom of the beaker is filtered to obtain a saturated calcium acetate aqueous solution.

[0052] (3) Take 10 g of styrene monomer and 50 mg of azobisisobutyronitrile in a conical flask, and ultrasonically dissolve them. Place the conical flask in a 75°C water bath and heat for 15 min, stop heating, and place the conical flask in cold water to cool to room temperature to terminate the reaction, and prepare a polystyrene prepolymer solution.

[0053] (4) Stir the saturated calcium acetate aqueous solution at a speed of 200 rpm, and drop the homogeneous solution into it to obtain water-based blasting beads. Continue to soak for 30 s, filter, rinse with deionized water to remove the residual calcium salt solution on the outer surface, and when the rinsing is completed, use filter paper to absorb the deionized water on the surface of the water-based blasting beads, and dry at room temperature.

[0054] (5) Place the surface-dried water-based blasting beads into the polystyrene prepolymer solution, soak for 30 s, take them out, place them on tin paper, and place them in a 50°C oven for 2 min, then take them out, so that the prepolymer on the surface of the water-based blasting beads solidifies, and a thin film is formed on the surface of the blasting beads.

[0055] (6) Repeat step (5) twice to obtain tobacco-flavored coated water-based blasting beads.

[0056] Example 2

[0057] This example provides a coated water-based blasting bead, and the preparation steps are as follows:

[0058] (1) Continuously add calcium chloride to the blueberry flavor, and stir with a glass rod while ultrasonically, until a small amount of calcium chloride precipitates at the bottom of the cup and does not dissolve anymore. Filter the excess precipitate at the bottom of the cup to obtain a saturated calcium chloride flavor solution.

[0059] Continuously add calcium chloride to the beaker containing deionized water, and stir while ultrasonically, until a small amount of calcium chloride precipitates at the bottom of the cup and does not dissolve anymore. Filter the excess precipitate at the bottom of the cup to obtain a saturated calcium chloride aqueous solution.

[0060] (2) Place 0.3 g of sodium alginate and 0.2 g of sodium ethylenediaminetetraacetate in 30 mL of deionized water, and fully stir to form a homogeneous solution at a speed of 300 rpm.

[0061] (3) Take 10 g of methyl methacrylate monomer and 45 mg of dibenzoyl peroxide initiator in a conical flask, and ultrasonically dissolve the initiator. Place the conical flask in a 70°C water bath and heat for 18 min, stop heating, and place the conical flask in cold water to cool to room temperature to terminate the reaction, and prepare a polymethyl methacrylate prepolymer solution.

[0062] (4) Drop saturated calcium chloride essence solution into the above homogeneous solution to form water-based burst beads, take out after soaking for about 30 s, and immediately put the taken-out burst beads into saturated calcium chloride aqueous solution stirred at a speed of 150 rpm, take out after soaking for 2 min, so that two layers of encapsulation are formed on the surface of the water-based burst beads.

[0063] (5) Put the encapsulated water-based burst beads into polymethyl methacrylate prepolymer solution, take out after soaking for about 40 s, place on tin paper, take out after baking in an oven at 60℃ for 1 min, so that the prepolymer on the surface of the burst beads is solidified and a layer of film is formed on the surface of the burst beads.

[0064] (6) Repeat step (5) for 3 times, and water-based burst beads coated with a layer of film are obtained.

[0065] Figure 1 It is a schematic diagram of the production process of the water-based burst beads coated with a layer of film in Example 1 of the present application. Figure 2 It is a schematic diagram of the production process of the water-based burst beads coated with a layer of film in Example 2 of the present application.

[0066] Figure 3 It is a finished product display diagram of the water-based burst beads coated with a layer of film produced in Example 1 of the present application. Figure 4 It is a finished product display diagram of the water-based burst beads coated with a layer of film produced in Example 2 of the present application.

[0067] Figure 5 It is an infrared spectrum diagram of sodium alginate before and after crosslinking with calcium ions, and the absorption peak of carbonyl group is shifted to the left, proving the successful crosslinking of calcium ions and sodium ions.

[0068] Figure 6 It is a schematic diagram of the production process of the water-based burst beads coated with a layer of film in Example 1 of the present application. Figure 7 It is a stability test of the water-based burst beads prepared in Example 1 and Example 2 of the present application before and after coating. After being placed at room temperature for three weeks, the weight loss rates of the water-based burst beads of Example 1 before and after coating are 45.4% and 3.6% respectively, and the weight loss rates of the water-based burst beads of Example 2 before and after coating are 15.4% and 2.2% respectively. After being encapsulated by the polymer, the stability of the burst beads is obviously improved. In addition, the stability of the burst beads prepared according to the method of Example 2 is greatly improved compared with Example 1.

[0069] Figure 8 It is a local EDS energy spectrum analysis of the water-based burst beads coated with a layer of film in Example 2 of the present application, and the local cross-section image (a) is a layered structure. In the element analysis image, the calcium element (c) is distributed in the whole area, and the sodium element (b) is distributed in the outside and overlaps with the calcium element, proving the crosslinking after the replacement of calcium ions and sodium ions.

[0070] In summary, the application prepares a new coated water-based burst bead, mainly through sodium ion and calcium ion exchange and cross-linking into a film structure to form a water-based burst bead, and then put it into a prepolymer solution of a polymer or a polymer solution with film-forming property to form a dense coating outside the burst bead, which not only greatly increases the loading capacity of the fragrance, but also plays a role in locking the moisture of the core material for a long time and increasing the strength of the burst bead.

[0071] The above merely illustrates the exemplary embodiments of the present application, and is not intended to limit the present application, and any modification, equivalent replacement and improvement within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing coated water-based burst beads, characterized in that, The specific steps are as follows: (1) Calcium salt is continuously added to water-soluble flavoring while sonicating and stirring until a saturated calcium salt flavoring solution is obtained; calcium salt is continuously added to deionized water while sonicating and stirring until a saturated calcium salt aqueous solution is obtained. (2) Sodium alginate and sodium carboxylate are mixed in deionized water and stirred thoroughly to form a homogeneous solution; in the homogeneous solution, the ratio of sodium alginate to deionized water is 0.3~2g:100mL, and the mass ratio of sodium alginate to sodium carboxylate is 1:0.5-2. (3) Mix the monomer and the initiator, sonicate until the initiator dissolves, and then heat in a water bath to obtain a prepolymer solution; the monomer of the prepolymer solution is methyl methacrylate, methyl acrylate, styrene or methyl styrene, the initiator is azobisisobutyronitrile or benzoyl peroxide, and the water bath heating temperature is 70 ℃-90 ℃ and the time is 15-30 min; (4) The saturated calcium salt fragrance solution is dropped into the homogeneous solution to form water-based burst beads. After soaking for 20-60 seconds, the beads are taken out and immediately placed in the saturated calcium salt aqueous solution for 1-5 minutes to form two layers of encapsulation on the surface of the water-based burst beads. (5) After immersing the encapsulated water-based burst beads in the prepolymer solution for 30-60 seconds, dry them to allow the prepolymer on the surface of the water-based burst beads to solidify and form a thin film. (6) Repeat step (5) 2 to 4 times to obtain coated water-based burst beads.

2. The preparation method according to claim 1, characterized in that: The sodium carboxylate is one or more of sodium carboxymethyl cellulose, sodium polyacrylate, sodium polymethacrylate, and sodium ethylenediaminetetraacetate.

3. The preparation method according to claim 1, characterized in that: The calcium salt is one or more of calcium chloride, calcium acetate, and calcium lactate.

4. A coated water-based bursting bead prepared by the preparation method according to any one of claims 1 to 3.

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