A biodegradable hot melt adhesive for the membrane seam of PET filter rod molding and its preparation method

Abstract

The application discloses a biodegradable hot melt adhesive for PET filter rod forming film joint, and raw materials for preparing the hot melt adhesive include 60-80 parts of resin, 1.5-3 parts of a compatibilizer, 20-30 parts of wax and 0-1.2 parts of an antioxidant by weight. The preparation method of the biodegradable hot melt adhesive for PET filter rod forming film joint comprises the following steps: S1, preheating a reaction kettle to 130-150 DEG C, adding an antioxidant and wax, and stirring for 10-20 min; S2, adding petroleum resin into the step S1, adjusting the rotating speed to 70-90 r / min, and stirring for 10-30 min; S3, adding EVA resin, degradable polyester resin and a compatibilizer into the step S1, uniformly stirring, vacuumizing, and controlling the pressure at 0.1-0.2 Mpa to remove bubbles; and S4, after the raw materials in the step S3 are removed of bubbles, underwater granulation is carried out after extrusion by a single screw extruder, the extrusion temperature is controlled at 105-110 DEG C, and the biodegradable filter rod joint hot melt adhesive is obtained.

Description

Technical Field

[0001] This invention relates to the technical field of C09J131 / 04, and more particularly to a biodegradable hot melt adhesive for the seam of PET filter rod molding membrane and its preparation method. Background Technology

[0002] In recent years, the tobacco industry has gradually shifted towards higher-end and more refined products. To enhance the aesthetics of cigarettes and improve the smoking experience, filter paper has evolved from ordinary filter paper to high-transparency filter paper, and now to the use of weakly polar transparent film materials such as PET. The biggest advantage of using PET as the filter film is its superior waterproof, moisture-proof, and seepage-proof properties. It allows for the addition of flavorings or other special substances like flavoring capsules within the filter, and it also preserves the aroma of burning cigarettes to a greater extent, providing smokers with a better smoking experience and a more refined appearance.

[0003] While there are numerous reports on the preparation and modification techniques of hot melt adhesives for cigarette filter connections, research on hot melt adhesives using PET film as the filter rod forming membrane is relatively limited. Compared to ordinary filter rod forming paper, PET film has a denser surface and lower surface energy. To improve its adhesion, surface treatment is required, such as electrical discharge machining, corona treatment, plasma treatment, or chemical oxidation, to impart active or highly polar groups like hydroxyl and carboxyl groups to the surface. However, these treatment methods are expensive and time-consuming, making them impractical for high-speed filter rod forming processes.

[0004] Chinese patent CN101538450B discloses a high-speed cigarette taper hot melt adhesive and its preparation method. This cigarette taper hot melt adhesive comprises the following components by weight: 25-35% ethylene-vinyl acetate copolymer, 35-45% tackifying resin, 20-40% viscosity modifier, 5-10% nano-silica, and 0.1-0.5% antioxidant. However, its compatibility with motors is not good.

[0005] Chinese patent CN103509488B discloses a high-speed cigarette sealing hot melt adhesive, which is composed of the following raw materials in parts by weight: ethylene-vinyl acetate copolymer 30-40, hydrogenated rosin resin 10-14, polyethylene wax 10-20, light calcium carbonate 2-3, hexadecyltrimethylammonium bromide 1-2, dioctyl ester 2-3, turpentine oil 3-5, 2-thiol-benzoimidazole 0.2-0.5, tris[2,4-di-tert-butylphenyl]phosphite 0.1-0.3, and tackifier 10-20. However, it is not suitable for bonding PET filter rod molding membranes.

[0006] Chinese patent CN201910923315 discloses a versatile cigarette packaging adhesive and its preparation method, which includes adding defoamers, preservatives, and additives to VAE emulsion and polyvinyl alcohol aqueous solution. It can adapt to the requirements of different packaging materials such as hard packs, soft packs, soft pack hardening, and slim cigarettes, with a flow rate of 300-1000 packs / minute, demonstrating wide applicability. However, its adhesion is not good enough. Summary of the Invention

[0007] To address the aforementioned issues, this application discloses a biodegradable hot melt adhesive for the seam of a PET filter rod molding membrane. By weight, the raw materials for preparing the hot melt adhesive include: 60-80 parts resin, 1.5-3 parts compatibilizer, 20-30 parts wax, and 0-1.2 parts antioxidant.

[0008] Preferably, the resin is selected from one or more of biodegradable polyester resin, petroleum resin, EVA resin, and polyolefin resin.

[0009] More preferably, the resin is a mixture of biodegradable polyester resin, petroleum resin, and EVA resin.

[0010] More preferably, the weight ratio of the biodegradable polyester resin, petroleum resin and EVA resin is 5:(18-38):(15-35).

[0011] More preferably, the melt index (2.16 kg, 190 °C) of the biodegradable polyester resin is 2-20 g / 10 min.

[0012] Preferably, the biodegradable polyester resin is selected from one or more of PCL, PBAT, PBS, PLA, PPC, and PHA.

[0013] More preferably, the biodegradable polyester resin is selected from one of PBAT, PBS, and PCL.

[0014] Preferably, the PBAT, brand name ECO-A05, is purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0015] Preferably, the PBS, brand name TH803S, is purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0016] Preferably, the PCL, grade 6800, is purchased from Perstorp in Sweden.

[0017] During the research process, the applicant discovered that the coating performance of hot melt adhesives is unstable and easily affected by ambient temperature, resulting in poor applicability on machines. Furthermore, when petroleum resin and EVA resin are mixed, the interaction between the two resins reduces the cohesive force of the system, leading to poor adhesion to PET materials. However, when biodegradable polyester resin is added to the system, especially when the weight ratio of biodegradable polyester resin, petroleum resin, and EVA resin is 5:(18-38):(15-35), the surface energy of the system is increased to 41-44 mN / m through enhanced intermolecular interactions, which is close to the surface energy of PET material.

[0018] Preferably, the petroleum resin is selected from one or more of aromatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, C5 hydrogenated petroleum resins, and C9 hydrogenated petroleum resins.

[0019] More preferably, the petroleum resin is a mixture of C5 hydrogenated petroleum resin and C9 hydrogenated petroleum resin in a weight ratio of (13-14):22.8, and more preferably in a weight ratio of 13.6:22.8.

[0020] Preferably, the C5 hydrogenated petroleum resin, grade C100W, is purchased from Eastman.

[0021] Preferably, the C9 hydrogenated petroleum resin, brand name FST-110, is purchased from Henghe Materials Technology Co., Ltd.

[0022] The applicant aims to prepare a hot melt adhesive with a surface energy close to that of PET material. The surface energy of PET material is 41-44 mN / m, while that of EVA resin is 25-31 mN / m, resulting in a surface energy of 36-56 mN / m for the EVA hot melt adhesive system. Existing EVA hot melt adhesive systems with higher surface energy typically incorporate rosin or modified rosin resin. These resins have strong odors that can affect the smoking experience of cigarettes, making them unsuitable for use in filter rod adhesives. Furthermore, using petroleum resins and hydrogenated petroleum resins cannot raise the surface energy of the EVA hot melt adhesive system to a level close to or greater than that of the PET filter rod membrane, resulting in poor adhesion to PET material.

[0023] Preferably, the EVA resin has a VA content of 19-33 wt% and a melt index of 150-800 g / 10 min.

[0024] More preferably, the EVA resin has a VA content of 28 wt% and a melt index of 800 g / 10 min.

[0025] Preferably, the EVA resin, grade 28800, is purchased from Eastman.

[0026] More preferably, the wax is selected from one or more of paraffin wax, Fischer-Tropsch wax, and polyethylene wax.

[0027] Preferably, the wax is Fischer-Tropsch wax, brand name SXH1, purchased from Sasol.

[0028] Preferably, the compatibilizer is selected from one or more of EsunBio5004K, silane coupling agents, titanate coupling agents, and aluminate coupling agents.

[0029] More preferably, the compatibilizer is EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0030] Preferably, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 168, and antioxidant 1076.

[0031] More preferably, the antioxidant is antioxidant 1010, purchased from BASF.

[0032] In one embodiment, the method for preparing the biodegradable hot melt adhesive for the PET filter rod forming membrane overlap includes the following steps:

[0033] S1: Preheat the reactor to 130-150℃, add antioxidants and wax, and stir for 10-20 minutes.

[0034] S2: Add petroleum resin to step S1, adjust the rotation speed to 70-90 r / min, and stir for 10-30 min.

[0035] S3: Add EVA resin, biodegradable polyester resin and compatibilizer to step S1, stir evenly and then vacuum, control the pressure at 0.1-0.2 MPa to remove air bubbles.

[0036] S4: After degassing the raw material in step S3, add it to a single screw extruder and extrude it. Set the extruder temperature according to the softening point of the material, and set the temperature to 105-110℃ for underwater granulation to obtain the filter rod joint hot melt adhesive.

[0037] Beneficial effects:

[0038] 1. This application proposes a partially biodegradable hot melt adhesive for the overlap of PET filter rod molding membrane and its preparation method. The hot melt adhesive of EVA system is modified by biodegradable polyester resin, which increases the adhesion to PET filter rod molding membrane without affecting the melt viscosity, softening point, open time and other indicators. The obtained filter rod overlap hot melt adhesive has biodegradable characteristics.

[0039] 2. The modified filter rod overlap hot melt adhesive of this application exhibits good applicability when used on ZL23 / ZL29 machines (machine speed 30-100 m / min) and has passed customer adhesion tests on PET filter rod forming films. Furthermore, the overlap hot melt adhesive obtained by this invention meets the requirements of standards such as YCT 187-2004 and YQ / T 84-2018.

[0040] 3. In this application, the weight ratio of biodegradable polyester resin, petroleum resin, and EVA resin is adjusted to 5:36.4:35. This enhances the interaction forces between molecules, resulting in a surface energy of 41-44 mN / m, which is close to that of PET material.

[0041] 4. This application modifies the EVA system hot melt adhesive to obtain a bonding hot melt adhesive that can be used for PET filter rod molding membrane and has degradable properties. It has stable coating performance, good adhesion performance, and degradable properties, making it more environmentally friendly.

[0042] 5. The hot melt adhesive prepared in this application has strong fast drying properties, which can meet the requirements of high-speed cigarette manufacturing. The hot melt adhesive is solvent-free, non-toxic, and has the characteristics of being non-hygroscopic, corrosion-resistant, and aging-resistant, making it easy to store and transport. Detailed Implementation

[0043] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0044] Example 1

[0045] The specific implementation method of the biodegradable hot melt adhesive for the membrane joint of the PET filter rod is as follows:

[0046] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0047] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0048] S3: Add 35 kg of EVA resin, 5 kg of PBAT, and 2 kg of compatibilizer to step S1, and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely mixed, perform a vacuum operation to remove air bubbles.

[0049] S4: The raw material from step S3 is added to a single-screw extruder and then granulated underwater to obtain PBAT-modified filter rod joint hot melt adhesive.

[0050] The PBAT, brand name ECO-A05, was purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0051] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0052] The EVA resin, brand name 28800, was purchased from Eastman.

[0053] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0054] The compatibilizer was EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0055] The antioxidant is antioxidant 1010, purchased from BASF.

[0056] Example 2

[0057] The specific implementation method of the biodegradable hot melt adhesive for the membrane joint of the PET filter rod is as follows:

[0058] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0059] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0060] S3: Add 35 kg of EVA resin, 5 kg of PBS, and 2 kg of compatibilizer to step S1, and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely mixed, perform a vacuum operation to remove air bubbles.

[0061] S4: The raw materials from step S3 are added to a single-screw extruder and then granulated underwater to obtain PBS-modified filter rod joint hot melt adhesive.

[0062] The PBS, brand name TH803S, was purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0063] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0064] The EVA resin, brand name 28800, was purchased from Eastman.

[0065] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0066] The compatibilizer was EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0067] The antioxidant is antioxidant 1010, purchased from BASF.

[0068] Example 3

[0069] The specific implementation method of the biodegradable hot melt adhesive for the membrane joint of the PET filter rod is as follows:

[0070] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0071] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0072] S3: Add 35 kg of EVA resin, 5 kg of PCL, and 2 kg of compatibilizer to step S1, and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely mixed, perform a vacuum operation to remove air bubbles.

[0073] S4: The raw material from step S3 is added to a single-screw extruder and then granulated underwater to obtain PCL-modified filter rod joint hot melt adhesive.

[0074] The PCL, grade 6800, was purchased from Perstorp in Sweden.

[0075] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0076] The EVA resin, brand name 28800, was purchased from Eastman.

[0077] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0078] The compatibilizer was EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0079] The antioxidant is antioxidant 1010, purchased from BASF.

[0080] Example 4

[0081] The method for implementing the partially biodegradable hot melt adhesive used for the membrane seam of the PET filter rod is as follows:

[0082] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0083] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0084] S3: Add 30 kg of EVA resin, 10 kg of PBS, and 2 kg of compatibilizer to step S1, and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely mixed, perform a vacuum operation to remove air bubbles.

[0085] S4: The raw materials from step S3 are added to a single-screw extruder and then granulated underwater to obtain PBS-modified filter rod joint hot melt adhesive.

[0086] The PBS, brand name TH803S, was purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0087] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0088] The EVA resin, brand name 28800, was purchased from Eastman.

[0089] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0090] The compatibilizer was EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0091] The antioxidant is antioxidant 1010, purchased from BASF.

[0092] Comparative Example 1

[0093] The specific implementation method of the hot melt adhesive for the membrane joint of the PET filter rod is as follows:

[0094] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0095] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0096] S3: Add 40 kg of EVA resin to step S1 and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely and uniformly mixed, perform a vacuuming operation to remove air bubbles.

[0097] S4: The raw materials from step S3 are added to a single-screw extruder and then extruded, followed by underwater granulation to obtain filter rod joint hot melt adhesive.

[0098] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0099] The EVA resin, brand name 28800, was purchased from Eastman.

[0100] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0101] The antioxidant is antioxidant 1010, purchased from BASF.

[0102] Comparative Example 2

[0103] The specific implementation method of the biodegradable hot melt adhesive for the membrane joint of the PET filter rod is as follows:

[0104] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0105] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0106] S3: Add 37 kg of EVA resin, 5 kg of PBS, and 2 kg of compatibilizer to step S1, and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely mixed, perform a vacuum operation to remove air bubbles.

[0107] S4: The raw materials from step S3 are added to a single-screw extruder and then granulated underwater to obtain PBS-modified filter rod joint hot melt adhesive.

[0108] The PBS, brand name TH803S, was purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0109] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0110] The EVA resin, brand name 28800, was purchased from Eastman.

[0111] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0112] The compatibilizer was EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0113] The antioxidant is antioxidant 1010, purchased from BASF.

[0114] Comparative Example 3

[0115] The method for implementing the partially biodegradable hot melt adhesive used for the membrane seam of the PET filter rod is as follows:

[0116] S1: Preheat the reactor to 140°C, add 600g of antioxidant 1010 and 23kg of Fischer-Tropsch wax, and start stirring for 15 minutes.

[0117] S2: Add 22.8 kg of hydrogenated C9 petroleum resin and 13.6 kg of hydrogenated C5 petroleum resin to S1, and start stirring at 80 r / min.

[0118] S3: Add 25 kg of EVA resin, 15 kg of PBS, and 2 kg of compatibilizer to step S1, and continue stirring until completely melted and uniformly mixed. After confirming that the system is completely mixed, perform a vacuum operation to remove air bubbles.

[0119] S4: The raw materials from step S3 are added to a single-screw extruder and then granulated underwater to obtain PBS-modified filter rod joint hot melt adhesive.

[0120] The PBS, brand name TH803S, was purchased from Xinjiang Lanshan Tunhe Polyester Co., Ltd.

[0121] The EVA resin has a VA content of 28wt% and a melt index of 800g / 10min.

[0122] The EVA resin, brand name 28800, was purchased from Eastman.

[0123] The Fischer-Tropsch wax, brand name SXH1, was purchased from Sasol.

[0124] The compatibilizer was EsunBio5004K, purchased from Shenzhen Guanghua Weiye Co., Ltd.

[0125] The antioxidant is antioxidant 1010, purchased from BASF.

[0126] Performance testing

[0127] 1. The hot melt adhesives prepared in Examples 1-4 and Comparative Examples 1-3 were tested for their monthly biodegradability using the soil burial method. A 10cm x 10cm square adhesive sample was weighed (m1) and buried in moist soil. Every month, the sample was removed, washed, dried, and weighed (m2). The rate of change in mass was used to characterize the degradation performance. The monthly degradation rate is:

[0128]

[0129] Where: α—monthly degradation rate

[0130] m1 and m2 represent the masses before and one month after degradation, respectively. Record the results in Table 1.

[0131] 2. Surface energy was measured using the OWRK contact angle method. The hot melt adhesives prepared in Examples 1-4 and Comparative Examples 1-3 were placed on release paper and baked in a 150°C oven. After cooling to room temperature, samples with a smooth surface were cut into 2cm x 1cm pieces for later use. The contact angles on the surface of the hot melt adhesive samples were then measured using deionized water and diiodomethane. The surface energy was then calculated, and the results are recorded in Table 1.

[0132] 3. The hot melt adhesives prepared in Examples 1-4 and Comparative Examples 1-3 were tested according to the following methods: melt viscosity test method (refer to HGT3660-1999); softening point test method (refer to GBT15332-1994); aging resistance test method (refer to GBT16998-1997); open time test method (refer to HGT3716-2003); tensile strength test method (refer to GB / T 528-1998), with a tensile rate of 50 mm / min. 3-5 standard samples were tested, and the average value was taken. The results are recorded in Table 1.

[0133] Table 1 Comparative test results of the examples and comparative examples

[0134]

[0135] As can be seen from Table 1, the hot melt adhesive with added biodegradable polyester did not affect its melt viscosity, softening point, open time, or bonding performance, and it also exhibited degradation characteristics.

[0136] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A biodegradable hot melt adhesive for a PET filter rod forming film tipping, characterized by, The preparation raw materials of the hot melt adhesive include, by weight parts, 60-80 parts of resin, 1.5-3 parts of compatibilizer, 20-30 parts of wax, and 0-1.2 parts of antioxidant; the resin is a mixture of degradable polyester resin, petroleum resin and EVA resin, the weight ratio of the degradable polyester resin, petroleum resin and EVA resin is 5: (18-38): (15-35); the melt index of the degradable polyester resin is 2-20 g / 10 min; the degradable polyester resin is selected from one of PBAT, PBS and PCL; the content of VA in the EVA resin is 19-33 wt%, and the melt index is 150-800 g / 10 min; the petroleum resin is a mixture of C5 hydrogenated petroleum resin and C9 hydrogenated petroleum resin, the weight ratio is (13-14): 22.8; the wax is Fischer-Tropsch wax; and the compatibilizer is EsunBio5004K.

2. A method of producing the hot melt adhesive according to claim 1, characterized by, The method comprises the following steps: S1: preheat the reaction kettle to 130-150℃, add antioxidant and wax, and stir for 10-20 min; S2: add petroleum resin to step S1, adjust the rotation speed to 70-90 r / min, and stir for 10-30 min; S3: add EVA resin, degradable polyester resin and compatibilizer to step S1, stir uniformly, vacuumize, control the pressure at 0.1-0.2 MPa, and remove bubbles; S4: after removing bubbles in step S3, add the raw materials to a single screw extruder, set the temperature of the extruder according to the softening point of the materials, the temperature setting range is 105-110℃, underwater pelletize, and obtain filter rod joint hot melt adhesive.

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