A gel-soft TPE covering sac material, its preparation method and application

Abstract

The present invention provides a gel soft TPE covering sac material, which is prepared from raw materials comprising the following components: 85 to 95 parts by weight of gel soft TPE material; 5 to 15 parts by weight of SAP water-absorbing resin; 0.1 to 0.5 parts by weight of initiator; the gel soft TPE material is prepared from raw materials comprising the following components: 20 to 30 parts by weight of SEBS1; 1 to 8 parts by weight of SEBS2; 1 to 8 parts by weight of SEBS-g-AA graft polymer; 65 to 75 parts by weight of white oil; 0.06 to 0.3 parts by weight of lubricant; 0.1 to 0.4 parts by weight of antioxidant. Compared with the prior art, the gel soft TPE covering sac material provided by the present invention adopts specific components with specific contents to achieve better overall interaction, and the obtained gel soft TPE covering sac material can significantly improve the defects of serious oil leakage and poor hydrophilicity of the TPE non-exhaust laryngeal mask, which stimulate the patient's throat and mucosa.

Description

Technical Field

[0001] The present invention relates to the technical field of gel TPE materials, and more specifically, to a gel soft TPE cover sac material and a preparation method thereof. Background Art

[0002] The most commonly used soft materials in the medical industry are PVC and silica gel; among them, the most commonly used plasticizer for soft PVC materials is bis(2-ethylhexyl) phthalate (DEHP). DEHP enters the human body through various routes such as oral, respiratory, intravenous infusion, and skin absorption, and harms the reproductive, circulatory, nervous and other systems of the human body. Silica gel is expensive, complex to process and requires vulcanization, and cannot be recycled. In contrast, styrene-ethylene / butene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), etc. are non-toxic and harmless, have excellent chemical resistance, good transparency of products, are gentle to human skin (no toxic side effects and allergic reactions), and in addition, their excellent soft touch on the skin can be used to manufacture medical supplies such as blood bags, baby pacifiers, various medical catheters, medical hoses, medical seals, gloves, surgical gowns, etc., meeting the hygiene standards of the US Food and Drug Administration (FDA). TPE replaces toxic PVC containing plasticizer (DEHP) with its environmentally friendly and non-toxic characteristics; TPE replaces silica gel materials with its advantages such as convenient processing, relatively low price, easy processing operation, short production cycle, recyclable scrap, no requirement for vulcanization, heat melting, and easy mixing with many additives. At present, the application of TPE replacing PVC and silica gel in the medical industry has been recognized by customers; medical-grade TPE can pass the biological, chemical, physical performance and other tests of medical testing institutions, and its easy adjustability of hardness and physical properties can better meet the requirements of different application medical devices, and has been widely used in disposable infusion storage medical devices.

[0003] The disposable non-venting laryngeal mask consists of two parts: a soft cover sac and an intubation tube. The cover sac part contacts the human throat and mucosa. The mainstream products of high-grade non-venting laryngeal masks sold on the market are made of silica gel. Compared with TPE material (SEBS), silica gel material is not only expensive, but also the product forming process is complex (vulcanization). Especially, soft silica gel is easy to be contaminated with dust during production and packaging, and it is very difficult to clean. The main components of the cover sac and intubation tube materials of TPE material are PP, SEBS and white oil. The materials are easy to purchase, have low cost, are easy to process, and are not easy to be contaminated with dust.

[0004] In summary, the laryngeal mask cover sac products made of soft PVC, soft silica gel and conventional soft TPE materials lack hydrophilicity and lack fitting degree when fitting with the human body, and the mucosal irritation will cause discomfort to the patient; and at present, SEBS oil-filled products on the market, including children's toys and medical devices, mostly have serious oil leakage problems due to low hardness and large oil filling amount. Summary of the Invention

[0005] In view of this, the object of the present invention is to provide a gel soft TPE cuff material, a preparation method and an application thereof. The gel soft TPE cuff material provided by the present invention can significantly improve the serious oil leakage and poor hydrophilicity defects of the TPE cuff without exhaust tube, which stimulate the patient's throat and mucosa.

[0006] The present invention provides a gel soft TPE cuff material, which is prepared from raw materials comprising the following components:

[0007] 85 to 95 parts by weight of gel soft TPE material;

[0008] 5 to 15 parts by weight of SAP water-absorbing resin;

[0009] 0.1 to 0.5 parts by weight of initiator;

[0010] The gel soft TPE material is prepared from raw materials comprising the following components:

[0011] 20 to 30 parts by weight of SEBS1;

[0012] 1 to 8 parts by weight of SEBS2;

[0013] 1 to 8 parts by weight of SEBS-g-AA graft polymer;

[0014] 65 to 75 parts by weight of white oil;

[0015] 0.06 to 0.3 parts by weight of slip agent;

[0016] 0.1 to 0.4 parts by weight of antioxidant.

[0017] Preferably, the styrene content of the SEBS1 is 12 wt% to 24 wt%, and the weight average molecular weight is 230,000 to 300,000; the styrene content of the SEBS2 is 12 wt% to 18 wt%, and the weight average molecular weight is 90,000 to 110,000, and it contains unsaturated polyisoprene chain segments, and the proportion of the polyisoprene chain segments is 10 wt% to 15 wt%.

[0018] Preferably, the preparation method of the SEBS-g-AA graft polymer is specifically as follows:

[0019] Under nitrogen protection, an initiator, acrylic monomer, and SEBS2 with a mass ratio of (0.5 - 0.8):(5 - 10):100 are mixed evenly in a high-speed mixer. Then, the mixture is added to a twin-screw extruder of a Haake torque rheometer for reactive grafting. The temperature from the feed port to the die of the extruder is set to 150°C - 200°C, and the die temperature is 160°C - 180°C. The grafted product blend is extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer.

[0020] Preferably, the white oil is selected from one or more of KN4010 naphthenic oil, No. 32 paraffin oil, and No. 36 paraffin oil;

[0021] The slip agent is selected from erucamide and / or oleamide;

[0022] The antioxidant is selected from pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and / or tris(2,4-di-tert-butylphenyl) phosphite.

[0023] Preferably, the preparation method of the gel soft TPE material is specifically as follows:

[0024] SEBS1, SEBS2, SEBS-g-AA graft polymer, white oil, slip agent, and antioxidant are mixed evenly in a high-speed mixer. Then, the mixture is left for 20h - 30h to allow the white oil to be fully absorbed. Next, the mixture is added to a co-rotating twin-screw extruder. The temperature from the feed port to the die of the extruder is set to 110°C - 160°C, the die temperature is 140°C - 160°C, and the screw speed is 200r / min - 300r / min. The blend is extruded through the die, pelletized, cooled, and dried to obtain the gel soft TPE material.

[0025] Preferably, the initiator is dicumyl peroxide.

[0026] The present invention also provides a preparation method of the gel soft TPE cover sac material described in the above technical solution, including the following steps:

[0027] The gel soft TPE material, SAP water-absorbing resin, and initiator are mixed evenly in a high-speed mixer, dried, packaged in an aluminum-plastic bag, and vacuum-sealed to obtain the gel soft TPE cover sac material.

[0028] The present invention also provides a disposable non-inflatable TPE laryngeal mask, which is prepared by a processing method of double-shot injection molding of the cover sac material and the intubation material. The cover sac material is the gel soft TPE cover sac material described in the above technical solution.

[0029] Preferably, the specific preparation process is as follows:

[0030] The intubation tube material is injection-molded at an injection temperature of 150°C to 180°C, an injection pressure of 20 MPa to 30 MPa, a holding pressure time of 20 s to 30 s, and a mold temperature of 20°C to 30°C to obtain the intubation tube part; the mold is rotated, and another injection molding unit is used to inject the cuff part, and overmolding is carried out at an injection temperature of 140°C to 170°C, an injection pressure of 20 MPa to 30 MPa, a holding pressure time of 20 s to 30 s, and a mold temperature of 20°C to 25°C. After cooling and ejecting for demolding, a single-use non-inflatable TPE laryngeal mask is obtained.

[0031] Preferably, the preparation process further includes:

[0032] The obtained single-use non-inflatable TPE laryngeal mask is packaged with a Tyvek sterilization bag and then irradiated and crosslinked with an electron beam of 10 KGy to 40 KGy.

[0033] The present invention provides a gel soft TPE cuff material, which is prepared from raw materials including the following components: 85 to 95 parts by weight of gel soft TPE material; 5 to 15 parts by weight of SAP water-absorbing resin; 0.1 to 0.5 parts by weight of initiator; the gel soft TPE material is prepared from raw materials including the following components: 20 to 30 parts by weight of SEBS1; 1 to 8 parts by weight of SEBS2; 1 to 8 parts by weight of SEBS-g-AA graft polymer; 65 to 75 parts by weight of white oil; 0.06 to 0.3 parts by weight of slip agent; 0.1 to 0.4 parts by weight of antioxidant. Compared with the prior art, the gel soft TPE cuff material provided by the present invention adopts specific components with specific contents to achieve good overall interaction, and the obtained gel soft TPE cuff material can significantly improve the defects of serious oil leakage and poor hydrophilicity existing in the TPE non-exhaust laryngeal mask, which stimulate the patient's throat and mucosa.

[0034] In addition, the preparation method provided by the present invention has a simple and easy process, which is convenient for scale-up production; at the same time, the main components of the prepared gel soft TPE cuff material are SEBS and white oil, which have the advantages of easy purchase of materials, low cost, easy processing, short production cycle, recyclable scraps, no requirement for vulcanization, meltability, easy mixing with many additives, etc. Moreover, the soft TPE is not easy to be contaminated with dust, reducing the production process and lowering the production cost, and has broad application prospects. Detailed Embodiments

[0035] Next, the technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0036] The present invention provides a gel soft TPE cover sac material, which is prepared from raw materials including the following components:

[0037] 85 to 95 parts by weight of gel soft TPE material;

[0038] 5 to 15 parts by weight of SAP water-absorbing resin;

[0039] 0.1 to 0.5 parts by weight of initiator;

[0040] The gel soft TPE material is prepared from raw materials including the following components:

[0041] 20 to 30 parts by weight of SEBS1;

[0042] 1 to 8 parts by weight of SEBS2;

[0043] 1 to 8 parts by weight of SEBS-g-AA graft polymer;

[0044] 65 to 75 parts by weight of white oil;

[0045] 0.06 to 0.3 parts by weight of lubricant;

[0046] 0.1 to 0.4 parts by weight of antioxidant.

[0047] In the present invention, the gel soft TPE cover sac material is prepared from raw materials including gel soft TPE material, SAP water-absorbing resin and initiator, and is preferably prepared from gel soft TPE material, SAP water-absorbing resin and initiator.

[0048] At present, general SEBS is a new type of thermoplastic elastomer prepared by selectively hydrogenating the unsaturated double bonds of the polybutadiene rubber segment in the thermoplastic block copolymer SBS. After hydrogenation, there are almost no unsaturated double bonds on the molecular chain of the product SEBS. Even under the action of an initiator and through electron beam irradiation, the degree of crosslinking between molecular chains is very low. In the present invention, through the adjustment of a specific combination of SEBS, the styrene content in the SEBS molecular chain is low, reducing the oil filling amount while increasing the double bond content in the chain segment of SEBS. During the electron beam irradiation sterilization process of the product, under the action of an initiator, the double bonds in the isoprene chain segment of SEBS break to generate free radicals, increasing the crosslinking degree between SEBS molecular chains and forming a micro-crosslinked network structure. The low oil filling amount and the existence of the network crosslinked structure can both reduce the oil seepage, and since the crosslinking degree is not high, it does not affect the processing performance of the material. At the same time, by adding SEBS-grafted acrylic materials and SAP water-absorbing resin, the hydrophilicity of the product is increased. The grafting of hydrophilic acrylic acid on the side chain of SEBS, the SEBS-g-AA graft polymer not only increases the hydrophilicity of the product, but also is a compatibilizer for SEBS and SAP water-absorbing resin, increasing the compatibility of the material; the increase in the hydrophilicity of the product improves the fitting property with the human body during the operation and the comfort of the patient. The present invention can significantly improve the serious defects of oil seepage and poor hydrophilicity existing in the TPE exhaust-free laryngeal mask through the selection of a specific SEBS combination, the addition of water-absorbing resin, and the subsequent micro-crosslinking process by electron beam irradiation sterilization.

[0049] In the present invention, the gel soft TPE material is prepared from raw materials including the following components:

[0050] SEBS1 20 parts by weight to 30 parts by weight;

[0051] SEBS2 1 part by weight to 8 parts by weight;

[0052] SEBS-g-AA graft polymer 1 part by weight to 8 parts by weight;

[0053] White oil 65 parts by weight to 75 parts by weight;

[0054] Slip agent 0.06 part by weight to 0.3 part by weight;

[0055] Antioxidant 0.1 part by weight to 0.4 part by weight;

[0056] Preferably, it is prepared from raw materials including the following components:

[0057] SEBS1 22.5 parts by weight to 25.5 parts by weight;

[0058] SEBS2 2.25 parts by weight to 4.5 parts by weight;

[0059] SEBS-g-AA graft polymer 1.5 parts by weight to 3 parts by weight;

[0060] 66 to 72 parts by weight of white oil;

[0061] 0.063 to 0.09 parts by weight of slip agent;

[0062] 0.18 parts by weight of antioxidant.

[0063] In the present invention, the styrene content of the SEBS1 is preferably 12 wt% to 24 wt%, and the weight-average molecular weight is preferably 230,000 to 300,000; the styrene content of the SEBS2 is preferably 12 wt% to 18 wt%, the weight-average molecular weight is preferably 90,000 to 110,000, and it contains unsaturated polyisoprene segments, and the proportion of the polyisoprene segments is preferably 10 wt% to 15 wt%. The present invention has no special restrictions on the sources of the SEBS1 and SEBS2, and commercially available products well-known to those skilled in the art can be used.

[0064] Soft PVC, soft TPE, and soft silicone material laryngeal mask products have problems such as poor fit with the human body and discomfort for patients due to lack of hydrophilicity; in response to this, the present invention uses SEBS oil filling to replace PVC and silicone to manufacture various soft medical consumables and medical devices; currently, Kraton G1641, G1642, and G1645 of Kraton Corporation (USA), SEPS SEPTON 4055 and HYBAR 7311 of Kuraray Co., Ltd. (Japan), Taixiang SEBS 8103, Taixiang SEBS DCP 029, and YH-506 of Baling Petrochemical are styrene thermoplastic elastomer base materials suitable for the preparation of medical devices; however, currently, most SEBS oil-filled ultra-soft products on the market, such as children's toys, have serious oil leakage problems because soft materials require a large amount of oil filling, and products made of SEBS after oil filling have the disadvantage of high oil leakage rate.

[0065] In the present invention, the preparation method of the SEBS-g-AA graft polymer is preferably specifically as follows:

[0066] Under nitrogen protection, an initiator, acrylic acid monomer, and SEBS2 with a mass ratio of (0.5 to 0.8):(5 to 10):100 are mixed evenly in a high-speed mixer, and then the mixture is added to a twin-screw extruder of a Haake torque rheometer for reaction grafting. The temperature from the feed port to the die of the extruder is set to 150°C to 200°C, and the die temperature is 160°C to 180°C. The graft product blend is extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer; wherein, the initiator is preferably dicumyl peroxide (DCP), and the SEBS2 is the same as in the above technical solution and will not be elaborated here; the present invention has no special restrictions on the sources of the initiator and acrylic acid monomer, and commercially available products well-known to those skilled in the art can be used.

[0067] The present invention uses SEBS2 to prepare SEBS-g-AA graft polymer, and the acrylic grafting rate of the prepared SEBS-g-AA graft polymer is preferably 2% to 5%.

[0068] In the present invention, the white oil is selected from one or more of KN4010 naphthenic oil, No. 32 paraffin oil and No. 36 paraffin oil, and more preferably No. 32 paraffin oil (the present invention is defined according to the basic concept in the industry that generally transparent oils are called white oils, and the commonly referred white oils usually include naphthenic oil, paraffin oil and aromatic oil); the slip agent is preferably selected from erucamide and / or oleamide, and more preferably erucamide; the antioxidant is preferably selected from pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010) and / or tris(2,4-di-tert-butylphenyl) phosphite (168), and more preferably pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010) and tris(2,4-di-tert-butylphenyl) phosphite (168); in the preferred embodiment of the present invention, the mass ratio of pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (1010) and tris(2,4-di-tert-butylphenyl) phosphite (168) is 1:1. The present invention has no special restrictions on the sources of the white oil, slip agent and antioxidant, and commercially available products well-known to those skilled in the art can be used.

[0069] In the present invention, the preparation method of the gel soft TPE material is preferably specifically as follows:

[0070] Mix SEBS1, SEBS2, SEBS-g-AA graft polymer, white oil, slip agent and antioxidant evenly in a high-speed mixer, then place the mixture for 20h to 30h to fully absorb the white oil, and then add the mixture into a co-rotating twin-screw extruder. Set the temperature from the feeding port to the die of the extruder to be 110°C to 160°C, the die temperature to be 140°C to 160°C, and the screw speed to be 200r / min to 300r / min. The blend is extruded through the die, pelletized, cooled and dried to obtain the gel soft TPE material;

[0071] More preferably:

[0072] Mix SEBS1, SEBS2, SEBS-g-AA graft polymer, white oil, slip agent and antioxidant evenly in a high-speed mixer, then place the mixture for 24h to fully absorb the white oil, and then add the mixture into a co-rotating twin-screw extruder. Set the temperature from the feeding port to the die of the extruder to be 110°C to 160°C, the die temperature to be 150°C, and the screw speed to be 250r / min. The blend is extruded through the die, pelletized, cooled and dried to obtain the gel soft TPE material.

[0073] In the present invention, the SAP super absorbent polymer is a new type of functional polymer material, which has a high water absorption function and excellent water retention performance. Since the super absorbent polymer is non-toxic, non-irritating to the human body, has no side reactions, and does not cause blood coagulation, it is suitable for application in the medical field.

[0074] In the present invention, the initiator is preferably dicumyl peroxide; commercially available products well-known to those skilled in the art can be used.

[0075] The TPE material cover sac material provided by the present invention is adjusted by a specific combination of SEBS to reduce the styrene content in the SEBS molecular chain, reduce the oil filling amount, and increase the double bond content in the SEBS chain segment. During the electron beam irradiation sterilization process of the product, under the action of the initiator, the double bonds in the polyisoprene chain segment of the specific SEBS break to generate free radicals, and the crosslinking degree between the SEBS molecular chains increases, forming a micro-crosslinked network structure. The low oil filling amount and the existence of the network crosslinked structure can both reduce the oil seepage. Since the crosslinking degree is not high and does not affect the processing performance of the material, by adding SEBS grafted acrylic material and SAP super absorbent polymer, the hydrophilicity of the product is increased, and the fit with the human body during the operation and the comfort of the patient are increased; among them, SEBS1 can be SEBS DCP029 of Taixiang Company, and SEBS2 can be SEBS YH-506 of Baling Petrochemical. The SEBS DCP029 powder has a high molecular weight, can fill a large amount of white oil and is not easy to precipitate, has a low styrene content, and the oil filling amount of the gel-like material obtained with the same hardness is lower than that of the SEBS powder with a high styrene content. SEBS YH-506 has a low styrene content and contains about 13% - 15% of unsaturated polyisoprene chain segments in the chain segment; the SAP super absorbent polymer can be Taisu BC 388S1 or BC 8001 of Formosa Plastics Corporation.

[0076] The present invention also provides a preparation method of the gel soft TPE cover sac material described in the above technical solution, including the following steps:

[0077] Mix the gel soft TPE material, SAP super absorbent polymer and initiator evenly in a high-speed mixer, dry, package in an aluminum-plastic bag, evacuate and seal to obtain the gel soft TPE cover sac material.

[0078] In the present invention, the gel soft TPE material, SAP super absorbent polymer and initiator are the same as those in the above technical solution, and will not be elaborated here.

[0079] The preparation method provided by the present invention has a simple and easy technological process, which is convenient for scale-up production. At the same time, the main components of the prepared gel soft TPE cuff material are SEBS and white oil, which have the advantages of easy material purchase, low cost, easy processing, short production cycle, recyclable scraps, no requirement for vulcanization, heat melting, easy mixing with many additives, etc. Moreover, the soft TPE is not easy to stain with dust, reducing the production process and production cost, and has broad application prospects.

[0080] The present invention also provides a disposable non-inflatable TPE laryngeal mask, which is prepared by a processing method of double-shot injection molding of the cuff material and the intubation material, and the cuff material is the gel soft TPE cuff material described in the above technical solution.

[0081] In the present invention, the preparation process uses two-color injection molding of the gel soft TPE cuff material and the intubation material. Preferably, specifically:

[0082] The intubation material is injection molded. The injection temperature is 150°C to 180°C, the injection pressure is 20 MPa to 30 MPa, the holding pressure time is 20 s to 30 s, and the mold temperature is 20°C to 30°C to obtain the intubation part. The mold is rotated, and another injection unit is used to inject the cuff part for overmolding. The injection temperature is 140°C to 170°C, the injection pressure is 20 MPa to 30 MPa, the holding pressure time is 20 s to 30 s, and the mold temperature is 20°C to 25°C. After cooling and ejecting the mold, a disposable non-inflatable TPE laryngeal mask is obtained.

[0083] In the present invention, the preparation process preferably further includes:

[0084] The obtained disposable non-inflatable TPE laryngeal mask is packaged with a Tyvek packaging sterilization bag and then irradiated and crosslinked by electron beam with an electron beam irradiation dose of 10 KGy to 40 KGy. During the sterilization of the product, under the action of an initiator, the double bonds of the isoprene chain segments of the SEBS molecular chain break to generate free radicals for crosslinking, forming a micro-crosslinked network structure, reducing the leakage of oil and improving the product performance;

[0085] More preferably:

[0086] The obtained disposable non-inflatable TPE laryngeal mask is packaged with a Tyvek packaging sterilization bag and then irradiated and crosslinked by electron beam with a dose of 20 KGy to 25 KGy.

[0087] At present, the high oil-filled SEBS materials sold on the market and the products prepared therefrom have the disadvantage of oil leakage; when the commercially available airless laryngeal mask cuff contacts the patient's throat and tracheal mucosa during use, the patient has discomfort; in order to overcome the defects of the existing high oil-filled TPE medical materials and their products, the present invention combines two specific SEBSs and, at the same time, cooperates with other components, including SEBS-grafted acrylic acid copolymer (SEBS-g-AA), white oil, slip agent, and antioxidant, to perform twin-screw extrusion granulation to obtain pellets. The material is mixed evenly with SAP water-absorbing resin and initiator to obtain a low-hardness gel-like TPE cuff material. The cuff material and the laryngeal mask intubation material are subjected to two-color injection molding to obtain an airless TPE laryngeal mask product. The product is sterilized by electron beam irradiation. At the same time of sterilization, micro-crosslinking of SEBS can be achieved to form a network crosslinked structure. By adjusting the specific combination of SEBSs, the product with a certain hardness has the advantage of low oil filling amount. At the same time, the SEBS micro-crosslinked network structure can not only prevent the obvious increase in the hardness of the cuff but also reduce the oil leakage; the hydrophilic groups of SEBS-g-AA and SAP resin increase the water absorption of the product and improve the comfort when the product fits with the patient's throat and tracheal mucosa. SEBS-g-AA can increase the compatibility between SEBS and SAP water-absorbing resin.

[0088] The present invention provides a gel soft TPE cuff material prepared from raw materials including the following components: 85 to 95 parts by weight of gel soft TPE material; 5 to 15 parts by weight of SAP water-absorbing resin; 0.1 to 0.5 parts by weight of initiator; the gel soft TPE material is prepared from raw materials including the following components: 20 to 30 parts by weight of SEBS1; 1 to 8 parts by weight of SEBS2; 1 to 8 parts by weight of SEBS-g-AA graft polymer; 65 to 75 parts by weight of white oil; 0.06 to 0.3 parts by weight of slip agent; 0.1 to 0.4 parts by weight of antioxidant. Compared with the prior art, the gel soft TPE cuff material provided by the present invention adopts specific components with specific contents to achieve good overall interaction, and the obtained gel soft TPE cuff material can significantly improve the serious oil leakage and poor hydrophilicity of the TPE airless laryngeal mask, which stimulate the patient's throat and mucosa.

[0089] In addition, the preparation method provided by the present invention has a simple and easy process and is convenient for large-scale production; at the same time, the main components of the prepared gel soft TPE cuff material are SEBS and white oil, which have the advantages of easy purchase of materials, low cost, easy processing, short production cycle, recyclability of scraps, no requirement for vulcanization, meltability, easy mixing and uniformity with many additives, etc. Moreover, the soft TPE is not easily contaminated with dust, reducing the production process and production cost, and has broad application prospects.

[0090] To further illustrate the present invention, the following examples are provided for detailed description. In the following examples / comparative examples of the present invention, unless otherwise specified, all reagents are of analytical grade and commercially available.

[0091] Example 1

[0092] Preparation of SEBS-g-AA graft polymer: Under nitrogen protection, 25 g of initiator dicumyl peroxide (DCP), 250 g of acrylic acid monomer, and 5 kg of SEBS YH-506 from Baling Petrochemical were mixed evenly in a high-speed mixer (stirred at 200 r / min for 30 min). Then, the mixture was added to a twin-screw extruder of a Haake torque rheometer for reactive grafting. The temperature from the feed port to the die of the extruder was set at 150 - 180 °C, the die temperature was 170 °C, and the screw speed was 200 r / min. The material was extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer.

[0093] Preparation of gel soft TPE material: 8.5 kg of SEBS DCP 029 from Taixiang, 1 kg of SEBS YH-506 from Baling Petrochemical, 0.5 kg of SEBS-g-AA, 24 kg of 32# paraffin oil, 21 g of erucamide L102, 30 g of antioxidant 1010, and 30 g of antioxidant 168 were added to a high-speed mixer and mixed evenly (stirred at 500 r / min for 30 min). Then, the mixture was left for 24 hours to allow the paraffin oil to be fully absorbed. Subsequently, the mixture was added to a co-rotating twin-screw extruder. The temperature from the feed port to the die of the extruder was set at 110 - 160 °C, the die temperature was 150 °C, and the screw speed was 250 r / min. The blend was extruded through the die, pelletized, cooled, and dried to obtain the gel soft TPE material.

[0094] Preparation of gel soft TPE capsule material: 9.2 kg of gel soft TPE material, 0.8 kg of SAP water-absorbing resin Taisu BC388S1, and 50 g of initiator DCP were mixed evenly in a high-speed mixer (stirred at 200 r / min for 20 min), dried at 50 °C, packaged in an aluminum-plastic bag, and vacuum-sealed to obtain the gel soft TPE capsule material.

[0095] The gel soft TPE cuff material and the intubation tube material are processed by double-material co-injection molding. The intubation tube material is injection-molded at an injection temperature of 150 - 180°C, an injection pressure of 25 MPa, a holding pressure time of 25 s, and a mold temperature of 30°C to obtain the intubation tube part. The mold is rotated, and another injection unit is used to inject the cuff part for overmolding at an injection temperature of 140 - 170°C, an injection pressure of 30 MPa, a holding pressure time of 30 s, and a mold temperature of 25°C. After cooling and ejecting for demolding, a single-use non-inflatable TPE laryngeal mask is obtained; the non-inflatable TPE laryngeal mask is packaged in a Tyvek sterilization bag and sterilized and cross-linked by electron beam irradiation at 25 ± 5 kGy.

[0096] Example 2

[0097] Preparation of SEBS-g-AA graft polymer: Under nitrogen protection, 30 g of initiator dicumyl peroxide (DCP), 400 g of acrylic acid monomer, and 5 kg of SEBS YH-506 from Baling Petrochemical are mixed evenly in a high-speed mixer (stirred at 200 r / min for 30 min). Then the mixture is added to a twin-screw extruder of a Haake torque rheometer for reactive grafting. The temperature from the feed port to the die of the extruder is set at 150 - 180°C, the die temperature is 170°C, the screw speed is 200 r / min. The material is extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer.

[0098] Preparation of gel soft TPE material: 8.0 kg of SEBS DCP 029 from Taixiang, 1.0 kg of SEBS YH-506 from Baling Petrochemical, 1.0 kg of SEBS-g-AA, 22 kg of 32# paraffin oil, 30 g of erucamide L102, 30 g of antioxidant 1010, and 30 g of antioxidant 168 are added to a high-speed mixer and mixed evenly (stirred at 500 r / min for 30 min). Then the mixture is left for 24 hours to allow the paraffin oil to be fully absorbed. Then the mixture is added to a co-rotating twin-screw extruder. The temperature from the feed port to the die of the extruder is set at 110 - 160°C, the die temperature is 150°C, and the screw speed is 250 r / min. The blend is extruded through the die, pelletized, cooled, and dried to obtain the gel soft TPE material.

[0099] Preparation of gel soft TPE cuff material: 9.0 kg of gel soft TPE material, 1.0 kg of SAP water-absorbing resin Taisu BC388S1, and 40 g of initiator DCP are mixed evenly in a high-speed mixer (stirred at 200 r / min for 20 min), dried at 50°C, packaged in an aluminum-plastic bag, and vacuum-sealed to obtain the gel soft TPE cuff material.

[0100] The gel-soft TPE cuff material and the intubation tube material are processed by double-material co-injection molding. The intubation tube material is injection-molded at an injection temperature of 150-180°C, an injection pressure of 30 MPa, a holding pressure time of 25 s, and a mold temperature of 30°C to obtain the intubation tube part. The mold is rotated, and the other injection unit is used to inject the cuff part for overmolding at an injection temperature of 140-170°C, an injection pressure of 30 MPa, a holding pressure time of 30 s, and a mold temperature of 25°C. After cooling and ejection demolding, a single-use non-inflatable TPE laryngeal mask is obtained; the non-inflatable TPE laryngeal mask is packaged in a Tyvek sterilization bag and sterilized by electron beam irradiation crosslinking at 25±5 kGy.

[0101] Example 3

[0102] Preparation of SEBS-g-AA graft polymer: Under nitrogen protection, 40 g of initiator dicumyl peroxide (DCP), 500 g of acrylic acid monomer, and 5 kg of SEBS YH-506 from Baling Petrochemical are mixed evenly in a high-speed mixer (stirred at 200 r / min for 30 min), and then the mixture is added to a twin-screw extruder of a Haake torque rheometer for reaction grafting. The temperature from the feeding port to the die of the extruder is set at 150-180°C, the die temperature is 170°C, the screw speed is 200 r / min, and the material is extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer.

[0103] Preparation of gel-soft TPE material: 7.5 kg of SEBS DCP 029 from Taixiang, 1.5 kg of SEBS YH-506 from Baling Petrochemical, 1.0 kg of SEBS-g-AA, 22 kg of 32# paraffin oil, 30 g of erucamide L102, 30 g of antioxidant 1010, and 30 g of antioxidant 168 are added to a high-speed mixer and mixed evenly (stirred at 500 r / min for 30 min). Then the mixture is left for 24 hours to allow the paraffin oil to be fully absorbed, and then the mixture is added to a co-rotating twin-screw extruder. The temperature from the feeding port to the die of the extruder is set at 110-160°C, the die temperature is 150°C, the screw speed is 250 r / min, and the blend is extruded through the die, pelletized, cooled, and dried to obtain the gel-soft TPE material.

[0104] Preparation of gel-soft TPE cuff material: 9.0 kg of gel-soft TPE material, 1.0 kg of SAP water-absorbing resin Taisu BC8001, and 40 g of initiator DCP are mixed evenly in a high-speed mixer (stirred at 200 r / min for 20 min), dried at 50°C, packaged in an aluminum-plastic bag, and vacuum-sealed to obtain the gel-soft TPE cuff material.

[0105] The gel-soft TPE cuff material and the cannula material are processed by double-material co-injection molding. The cannula material is injection molded at an injection temperature of 150-180°C, an injection pressure of 25 MPa, a holding pressure time of 30 s, and a mold temperature of 30°C to obtain the cannula part. The mold is rotated, and the other injection unit is used to inject the cuff part for overmolding at an injection temperature of 140-170°C, an injection pressure of 30 MPa, a holding pressure time of 25 s, and a mold temperature of 25°C. After cooling and ejecting demolding, a disposable non-inflatable TPE laryngeal mask is obtained; the non-inflatable TPE laryngeal mask is packaged in a Tyvek packaging sterilization bag and sterilized and crosslinked by electron beam irradiation at 25±5 kGy.

[0106] Example 4

[0107] Preparation of SEBS-g-AA graft polymer: Under nitrogen protection, 30 grams of initiator dicumyl peroxide (DCP), 300 grams of acrylic acid monomer, and 5 kilograms of SEBS YH-506 from Baling Petrochemical are mixed evenly in a high-speed mixer (stirred at 200 r / min for 30 min), and then the mixture is added to a twin-screw extruder of a Haake torque rheometer for reactive grafting. The temperature from the feed port to the die of the extruder is set at 150-180°C, the die temperature is 170°C, the screw speed is 250 r / min, and the material is extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer.

[0108] Preparation of gel-soft TPE material: 8.5 kilograms of SEBS DCP 029 from Taixiang, 0.75 kilograms of SEBS YH-506 from Baling Petrochemical, 0.75 kilograms of SEBS-g-AA, 23 kilograms of 32# paraffin oil, 30 grams of erucamide L102, 30 grams of antioxidant 1010, and 30 grams of antioxidant 168 are added to a high-speed mixer and mixed evenly (stirred at 500 r / min for 30 min). Then the mixture is left for 24 hours to allow the paraffin oil to be fully absorbed, and then the mixture is added to a co-rotating twin-screw extruder. The temperature from the feed port to the die of the extruder is set at 110-160°C, the die temperature is 150°C, the screw speed is 250 r / min, and the blend is extruded through the die, pelletized, cooled, and dried to obtain the gel-soft TPE material.

[0109] Preparation of gel-soft TPE cuff material: 9.5 kilograms of gel-soft TPE material, 0.5 kilograms of SAP water-absorbing resin Taisu BC8001, and 30 grams of initiator DCP are mixed evenly in a high-speed mixer (stirred at 200 r / min for 20 min), dried at 50°C, packaged in an aluminum-plastic bag, and vacuum-sealed to obtain the gel-soft TPE cuff material.

[0110] The gel-soft TPE cuff material and the cannula material are processed by two-material co-injection molding. The cannula material is injection molded at an injection temperature of 150 - 180 °C, an injection pressure of 25 MPa, a holding pressure time of 25 s, and a mold temperature of 30 °C to obtain the cannula part. Then the mold is rotated, and another injection unit is used to inject the cuff part for overmolding at an injection temperature of 140 - 170 °C, an injection pressure of 30 MPa, a holding pressure time of 30 s, and a mold temperature of 25 °C. After cooling and ejecting for demolding, a disposable non-inflatable TPE laryngeal mask is obtained. The non-inflatable TPE laryngeal mask is packaged in a Tyvek sterilization bag and sterilized by electron beam irradiation cross-linking at 25 ± 5 kGy.

[0111] Comparative Example 1

[0112] Preparation of soft TPE cuff material: 10 kg of SEBS YH-503H from Baling Petrochemical, 30 kg of 32# paraffin oil, 40 g of initiator DCP, 30 g of erucic acid amide L102, 30 g of antioxidant 1010, and 30 g of antioxidant 168 are added to a high-speed mixer and mixed evenly (stirred at 500 r / min for 30 min). Then the mixture is left for 24 hours to allow the paraffin oil to be fully absorbed. After that, the mixture is added to a co-rotating twin-screw extruder. The temperature from the feeding port to the die of the extruder is set at 110 - 160 °C, the die temperature is 150 °C, and the screw speed is 250 r / min. The blend is extruded through the die, pelletized, cooled, and dried to obtain the soft TPE cuff material.

[0113] The soft TPE cuff material and the cannula material are processed by two-material co-injection molding. The cannula material is injection molded at an injection temperature of 150 - 180 °C, an injection pressure of 30 MPa, a holding pressure time of 30 s, and a mold temperature of 30 °C to obtain the cannula part. Then the mold is rotated, and another injection unit is used to inject the cuff part for overmolding at an injection temperature of 140 - 170 °C, an injection pressure of 30 MPa, a holding pressure time of 30 s, and a mold temperature of 25 °C. After cooling and ejecting for demolding, a disposable non-inflatable TPE laryngeal mask is obtained. The non-inflatable TPE laryngeal mask is packaged in a Tyvek sterilization bag and sterilized by electron beam irradiation at 25 ± 5 kGy.

[0114] Comparative Example 2

[0115] Preparation of soft TPE bladder material: 10 kg of SEBS YH-503H from Baling Petrochemical, 28 kg of 32# paraffin oil, 40 g of initiator DCP, 21 g of erucamide L102, 30 g of antioxidant 1010, and 30 g of antioxidant 16830 were added to a high-speed mixer and mixed evenly (stirred at 500 r / min for 30 min). After that, the mixture was left for 24 hours to allow the paraffin oil to be fully absorbed. Then, the mixture was added to a co-rotating twin-screw extruder. The temperature from the feeding port to the die of the extruder was set at 110 - 160 °C, the die temperature was 150 °C, and the screw speed was 250 r / min. The blend was extruded through the die, pelletized, cooled, and dried to obtain the soft TPE bladder material.

[0116] The soft TPE bladder material and the cannula material were processed by double-material co-injection molding. The cannula material was injection-molded at an injection temperature of 150 - 180 °C, an injection pressure of 30 MPa, a holding pressure time of 30 s, and a mold temperature of 30 °C to obtain the cannula part. The mold was rotated, and the bladder part was injection-molded using another injection unit for overmolding. The injection temperature was 140 - 170 °C, the injection pressure was 25 MPa, the holding pressure time was 25 s, and the mold temperature was 25 °C. After cooling and ejecting from the mold, a disposable non-inflatable TPE laryngeal mask was obtained. The non-inflatable TPE laryngeal mask was packaged in a Tyvek sterilization bag and sterilized by electron beam irradiation at 25 ± 5 KGy.

[0117] Performance testing:

[0118] The soft TPE bladder materials and the disposable non-inflatable TPE laryngeal masks prepared in Examples 1 - 4 and Comparative Examples 1 - 2 were subjected to performance testing, and the results are shown in Table 1.

[0119] Table 1 Performance test data table provided by the present invention

[0120]

[0121]

[0122] It can be seen from the performance test data in Table 1 that when the hardness is not much different, the white oil weight ratio of the bladder material in Examples 1 - 4 is significantly less than that in Comparative Examples 1 - 2. Through the adjustment of a specific SEBS composition and electron beam irradiation sterilization crosslinking, the oil leakage rate of the product is significantly reduced, the gel content of the product increases, a micro-crosslinked network structure is formed, the water-absorbing resin increases the hydrophilicity of the material, and the contact angle with water becomes smaller. Among them, the comprehensive performance of the material and product in Example 3 is the best.

[0123] The foregoing description of the disclosed embodiments enables those skilled in the art to practice or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A gel soft TPE bladder material is prepared from raw materials comprising the following components: 85 to 95 parts by weight of gel soft TPE material; 5 to 15 parts by weight of SAP water-absorbing resin; 0.1 to 0.5 parts by weight of initiator; The gel soft TPE material is prepared from raw materials comprising the following components: 20 to 30 parts by weight of SEBS1; 1 to 8 parts by weight of SEBS2; 1 to 8 parts by weight of SEBS-g-AA graft polymer; 65 to 75 parts by weight of white oil; 0.06 to 0.3 parts by weight of slip agent; 0.1 to 0.4 parts by weight of antioxidant; The styrene content of the SEBS1 is 12wt% - 24wt%, and the weight-average molecular weight is 230,000 - 300,000; the styrene content of the SEBS2 is 12wt% - 18wt%, and the weight-average molecular weight is 90,000 - 110,000, and it contains unsaturated polyisoprene chain segments, and the proportion of the polyisoprene chain segments is 10wt% - 15wt%; The preparation method of the SEBS-g-AA graft polymer is specifically as follows: Under nitrogen protection, an initiator, acrylic acid monomer, and SEBS2 with a mass ratio of (0.5 - 0.8):(5 - 10):100 are mixed evenly in a high-speed mixer, and then the mixture is added to a twin-screw extruder of a Haake torque rheometer for reaction grafting. The temperature from the feed port to the die of the extruder is set at 150°C - 200°C, and the die temperature is 160°C - 180°C. The grafted product blend is extruded through the die, air-cooled, pelletized, and dried to obtain the SEBS-g-AA graft polymer.

2. The gel soft TPE cover bladder material according to claim 1, wherein The white oil is selected from one or more of KN4010 naphthenic oil, No. 32 paraffin oil, and No. 36 paraffin oil; The slip agent is selected from erucamide and / or oleamide; The antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and / or tris(2,4-di-tert-butylphenyl) phosphite.

3. The gel soft TPE cover sac material according to claim 1, characterized in that, The preparation method of the gel soft TPE material is specifically as follows: SEBS1, SEBS2, SEBS-g-AA graft polymer, white oil, slip agent, and antioxidant are mixed evenly in a high-speed mixer, and then the mixture is placed for 20h - 30h to allow the white oil to be fully absorbed. Then the mixture is added to a co-rotating twin-screw extruder. The temperature from the feed port to the die of the extruder is set at 110°C - 160°C, the die temperature is 140°C - 160°C, and the screw speed is 200r / min - 300r / min. The blend is extruded through the die, pelletized, cooled, and dried to obtain the gel soft TPE material.

4. The gel soft TPE cover sac material according to claim 1, wherein The initiator is dicumyl peroxide.

5. A preparation method of the gel soft TPE bladder material according to any one of claims 1 - 4, comprising the following steps: The gel soft TPE material, SAP water-absorbing resin, and initiator are mixed evenly in a high-speed mixer, dried, packaged in an aluminum-plastic bag, and vacuum-sealed to obtain the gel soft TPE bladder material.

6. A disposable non-inflatable TPE laryngeal mask is prepared by a processing method of double-material co-injection molding of a mask bladder material and an intubation material, and is characterized in that, The bladder material is the gel soft TPE bladder material according to any one of claims 1 - 4.

7. The disposable non-inflatable TPE laryngeal mask according to claim 6, characterized in that, The specific preparation process is as follows: The intubation tube material is injection molded at an injection temperature of 150°C to 180°C, an injection pressure of 20 MPa to 30 MPa, a holding pressure time of 20 s to 30 s, and a mold temperature of 20°C to 30°C to obtain the intubation tube part; the mold is rotated, and another injection molding unit is used to inject the cuff part for overmolding. The injection temperature is 140°C to 170°C, the injection pressure is 20 MPa to 30 MPa, the holding pressure time is 20 s to 30 s, and the mold temperature is 20°C to 25°C. After cooling and ejecting the mold, a single-use non-inflatable TPE laryngeal mask is obtained.

8. The disposable non-inflatable TPE laryngeal mask according to claim 7, characterized in that, The preparation process also includes: The obtained single-use non-inflatable TPE laryngeal mask is packaged with a Tyvek sterilization bag and then sterilized and crosslinked by electron beam irradiation at 10 kGy to 40 kGy.

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