WO2024021182A1 - Self-healing tpu hot melt adhesive film and preparation method therefor - Google Patents

Self-healing tpu hot melt adhesive film and preparation method therefor Download PDF

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Publication number
WO2024021182A1
WO2024021182A1 PCT/CN2022/112221 CN2022112221W WO2024021182A1 WO 2024021182 A1 WO2024021182 A1 WO 2024021182A1 CN 2022112221 W CN2022112221 W CN 2022112221W WO 2024021182 A1 WO2024021182 A1 WO 2024021182A1
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Prior art keywords
self
healing
melt adhesive
hot melt
adhesive film
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PCT/CN2022/112221
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French (fr)
Chinese (zh)
Inventor
宾家荃
宾家齐
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广东汇齐新材料有限公司
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Publication of WO2024021182A1 publication Critical patent/WO2024021182A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Definitions

  • the invention relates to the field of hot-melt adhesive film materials, and in particular to a self-healing TPU hot-melt adhesive film and a preparation method thereof.
  • Polymer-based composite materials with self-healing function can imitate the self-healing mechanism of biological damage to self-repair material processing or microscopic cracks that are difficult to detect with the naked eye during use.
  • Self-healing materials have a wide range of applications, including military equipment, electronic products, automobiles, aircraft, building materials and other fields.
  • the ultimate goal is to improve the adhesive force of the adhesive film.
  • the adhesive film itself is damaged, such as cracks or breaks, on the one hand, it will cause a rapid decrease in the adhesive peeling force.
  • Existing repair technology can be used to online Repairing defects such as damage or cracks in the packaging film is complicated and cumbersome, and the repair cost is high.
  • the present invention provides a self-healing TPU hot-melt adhesive film that realizes rapid repair of products.
  • the invention also provides a method for preparing a self-repairing TPU hot-melt adhesive film with a simple and convenient process.
  • a self-healing TPU hot-melt adhesive film includes the following raw materials in parts by weight: 80-100 parts of TPU particles; 20-43 parts of nitrile rubber; 5-8 parts of self-healing supramolecular compounds; 2-4 parts of cross-linking agent; 1-2 parts of UV stabilizer; 0.5-2 parts of tackifier.
  • melt flow index of the TPU particles is 0.5-40g/10min.
  • nitrile rubber is one or more mixtures of nitrile rubber, hydrogenated nitrile rubber or carboxyl nitrile rubber without special treatment.
  • the self-healing supramolecular compound is an olefin amide-containing polysiloxane or a self-polymer of a polysilsesquioxane monomer.
  • cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-butyl-4,4-di(tert-amyl peroxybenzoate)
  • the cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-butyl-4,4-di(tert-amyl peroxybenzoate)
  • the cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-butyl-4,4-di(tert-amyl peroxybenzoate)
  • UV light stabilizer is 2-hydroxy-5-chlorobenzophenone, 2,2′-tetramethylenebis(3,1-benzoxazine-4- ketone), 2-hydroxy-4-benzoyloxybenzophenone, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2,2′,4,4 ′-One or a mixture of two or more tetrahydroxybenzophenones.
  • tackifier is 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy) One of the silane and vinyltriethoxysilane.
  • a method for preparing a self-healing TPU hot melt adhesive film including the following steps:
  • step S2 Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets;
  • step S3 Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film.
  • the casting temperature is 120-140°C.
  • a further improvement to the above technical solution is that in the S1 step, the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5-8 minutes.
  • a further improvement to the above technical solution is that in the S2 step, the extrusion temperature is 150-170°C and the stirring speed is 660-850r/min.
  • the present invention uses self-repairing supramolecular compounds to introduce into the TPU polymer molecular chain. Due to the self-polymerization of polysiloxane or polysilsesquioxane monomers of olefin amide, a hydrogen bond cross-linked network is formed in the TPU polymer. Through the breaking and healing of hydrogen bonds, the material has good self-healing ability and special properties such as repeatable processing and active self-healing, thereby reducing the tediousness of online repair operations, reducing repair costs, and improving products. service life and efficiency.
  • a self-healing TPU hot-melt adhesive film includes the following raw materials in parts by weight: 80-100 parts of TPU particles; 20-43 parts of nitrile rubber; 5-8 parts of self-healing supramolecular compounds; 2-4 parts of cross-linking agent; 1-2 parts of UV stabilizer; 0.5-2 parts of tackifier.
  • melt flow index of the TPU particles is 0.5-40g/10min.
  • nitrile rubber is a mixture of one or more of nitrile rubber, hydrogenated nitrile rubber or carboxyl nitrile rubber without special treatment.
  • the self-healing supramolecular compound is an olefin amide-containing polysiloxane or a self-polymer of a polysilsesquioxane monomer.
  • the preparation method of self-healing supramolecular compounds includes the following steps: under room temperature stirring conditions, dissolve polysiloxane or polysilsesquioxane with an active amino structure in a methylene chloride solution, and add olefin acyl chloride compounds in sequence , Activator, synthesis reaction at room temperature for 10-20 hours, in which the molar ratio of amino-structured polysiloxane or polysilsesquioxane to olefin acyl chloride-based compounds is 10:11-15, and the activator and olefin acyl chloride-based compounds are The mass ratio of the compounds is 1:5-10.
  • the material is added to 0.1-1mol/L sodium hydroxide solution for alkaline washing, and then added to 0.5-1mol/L dilute hydrochloric acid solution for acid washing and 0.5-1mol/L.
  • L magnesium chloride solution is washed with salt, then separated into layers, the organic phase is dried, and the solvent is removed to obtain a self-healing supramolecular compound.
  • the cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-butyl-4,4-di(tert-butylperoxy)pentyl
  • tert-amyl benzoate tert-butyl peroxybenzoate
  • tert-amyl peroxybenzoate tert-amyl peroxybenzoate
  • n-butyl-4,4-di(tert-butylperoxy)pentyl One or a mixture of acid esters and ethyl-3,3-di(tert-butyl peroxy)butyrate.
  • the UV light stabilizer is 2-hydroxy-5-chlorobenzophenone, 2,2′-tetramethylene bis(3,1-benzoxazin-4-one), 2-hydroxy ⁇ 4 ⁇ benzoyloxybenzophenone, 2 ⁇ (2 ⁇ hydroxy ⁇ 3,5 ⁇ di ⁇ tert ⁇ pentylphenyl)benzotriazole, 2,2′,4,4′ ⁇ tetrahydroxydiphenyl One or a mixture of two or more ketones.
  • the tackifier is 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane One of the oxysilanes.
  • a method for preparing a self-healing TPU hot melt adhesive film including the following steps:
  • step S2 Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets;
  • step S3 Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film.
  • the casting temperature is 120-140°C.
  • the melting temperature is 135-150°C
  • the stirring speed is 150-200r/min
  • the stirring time is 5-8 minutes.
  • the extrusion temperature is 150-170°C
  • the stirring speed is 660-850r/min.
  • a method for preparing a self-healing TPU hot melt adhesive film including the following steps:
  • step S2 Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets; the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min;
  • step S3 Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film.
  • the casting temperature is 120-140°C.
  • a method for preparing a self-healing TPU hot melt adhesive film including the following steps:
  • step S2 Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets; the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min;
  • step S3 Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film.
  • the casting temperature is 120-140°C.
  • a method for preparing a self-healing TPU hot melt adhesive film including the following steps:
  • step S2 Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets; the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min;
  • step S3 Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film.
  • the casting temperature is 120-140°C.
  • Example 1 Repeat the preparation method of Example 1 according to the specified proportions of each component, but do not add or use the self-healing supramolecular compound.
  • Example 2 Repeat the preparation method of Example 2 according to the specified proportions of each component, but do not add or use the self-healing supramolecular compound.
  • Example 3 Repeat the preparation method of Example 3 according to the specified proportions of each component, but do not add or use the self-healing supramolecular compound.
  • the properties of the hot melt adhesive film in the embodiment are shown in Table 1, in which the self-healing ability refers to the self-healing ability after being scratched by a knife and the recovery ability after deformation after bending.
  • the self-healing ability is the adhesive film after being scratched or deformed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Disclosed is a self-healing TPU hot melt adhesive film, comprising the following raw materials in parts by weight: 80-100 parts of a TPU particle; 20-43 parts of nitrile rubber; 5-8 parts of a self-healing supramolecular compound; 2-4 parts of a cross-linking agent; 1-2 parts of an ultraviolet light stabilizer; and 0.5-2 parts of a tackifier. In addition, provided is a self-healing TPU hot melt adhesive film for realizing rapid healing of a product; and further provided is a preparation method for a self-healing TPU hot melt adhesive film. According to the method, the process is simple and convenient.

Description

一种自修复TPU热熔胶膜及其制备方法A self-healing TPU hot melt adhesive film and its preparation method
相关申请的交叉引用。Cross-references to related applications.
本申请要求于2022年7月29日提交中国专利局，申请号为202210912188.1，发明名称为“一种自修复TPU热熔胶膜及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requests the priority of the Chinese patent application submitted to the China Patent Office on July 29, 2022, with the application number 202210912188.1, and the invention name is "A self-healing TPU hot melt adhesive film and its preparation method", and its entire content is approved This reference is incorporated into this application.
技术领域Technical field
本发明涉及热熔胶膜材料领域，特别是涉及一种自修复TPU热熔胶膜及其制备方法。The invention relates to the field of hot-melt adhesive film materials, and in particular to a self-healing TPU hot-melt adhesive film and a preparation method thereof.
背景技术Background technique
具有自修复功能的聚合物基复合材料可以模仿生物体损伤自愈合的机理对材料加工或对使用过程中肉眼难以发现的微观裂纹进行自修复。而自修复材料的应用范围极为广泛，包括军用装备、电子产品、汽车、飞机、建筑材料等领域。Polymer-based composite materials with self-healing function can imitate the self-healing mechanism of biological damage to self-repair material processing or microscopic cracks that are difficult to detect with the naked eye during use. Self-healing materials have a wide range of applications, including military equipment, electronic products, automobiles, aircraft, building materials and other fields.
技术问题technical problem
目前，以提高胶膜的粘结力为最终目的，但当胶膜本身出现破损如裂痕或断裂等现象时，一方面会造成粘结剥离力的极速下降，而利用现有的修复技术来在线修复封装胶膜的破损或裂痕等缺陷，一方面操作程序复杂繁琐，另一方面修复成本较高。At present, the ultimate goal is to improve the adhesive force of the adhesive film. However, when the adhesive film itself is damaged, such as cracks or breaks, on the one hand, it will cause a rapid decrease in the adhesive peeling force. Existing repair technology can be used to online Repairing defects such as damage or cracks in the packaging film is complicated and cumbersome, and the repair cost is high.
技术解决方案Technical solutions
为解决上述技术问题，本发明提供一种实现产品的快速修复的自修复TPU热熔胶膜。In order to solve the above technical problems, the present invention provides a self-healing TPU hot-melt adhesive film that realizes rapid repair of products.
本发明还提供一种自修复TPU热熔胶膜的制备方法，工艺简单便捷。The invention also provides a method for preparing a self-repairing TPU hot-melt adhesive film with a simple and convenient process.
本发明采用如下技术方案：The present invention adopts the following technical solutions:
一种自修复TPU热熔胶膜，包括如下重量份的原料：TPU颗粒80‐100份；丁腈橡胶20‐43份；自修复超分子化合物5‐8份；交联剂2‐4份；紫外光稳定剂1‐2份；增粘剂0.5‐2份。A self-healing TPU hot-melt adhesive film includes the following raw materials in parts by weight: 80-100 parts of TPU particles; 20-43 parts of nitrile rubber; 5-8 parts of self-healing supramolecular compounds; 2-4 parts of cross-linking agent; 1-2 parts of UV stabilizer; 0.5-2 parts of tackifier.
对上述技术方案的进一步改进为，所述TPU颗粒的熔融流动指数为0.5‐40g/10min。A further improvement to the above technical solution is that the melt flow index of the TPU particles is 0.5-40g/10min.
对上述技术方案的进一步改进为，所述丁腈橡胶为未经特殊处理的丁腈橡胶、 氢化丁腈橡胶或羧基丁腈橡胶中的一种或多种的混合物。A further improvement to the above technical solution is that the nitrile rubber is one or more mixtures of nitrile rubber, hydrogenated nitrile rubber or carboxyl nitrile rubber without special treatment.
对上述技术方案的进一步改进为，所述自修复超分子化合物为含烯烃酰胺的聚硅氧烷或聚倍半硅氧烷单体的自聚物。A further improvement to the above technical solution is that the self-healing supramolecular compound is an olefin amide-containing polysiloxane or a self-polymer of a polysilsesquioxane monomer.
对上述技术方案的进一步改进为，所述交联剂为苯甲酸叔戊酯、叔丁基过氧化苯甲酸酯、过氧化苯甲酸叔戊酯、正丁基‐4，4‐二(叔丁基过氧化)戊酸酯、乙基‐3，3‐二(叔丁基过氧化)丁酸酯中的一种或几种的混合物。A further improvement to the above technical solution is that the cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-butyl-4,4-di(tert-amyl peroxybenzoate) One or a mixture of butyl peroxy)valerate and ethyl-3,3-di(tert-butyl peroxy)butyrate.
对上述技术方案的进一步改进为，所述紫外光稳定剂为2‐羟基‐5‐氯二苯甲酮、2，2′‐四亚甲基双(3，1‐苯并噁嗪‐4‐酮)、2‐羟基‐4‐苯甲酰基氧基二苯甲酮、2‐(2‐羟基‐3，5‐二叔戊基苯基)苯并三唑、2，2′，4，4′‐四羟基二苯甲酮的一种或者两种以上的混合物。A further improvement to the above technical solution is that the UV light stabilizer is 2-hydroxy-5-chlorobenzophenone, 2,2′-tetramethylenebis(3,1-benzoxazine-4- ketone), 2-hydroxy-4-benzoyloxybenzophenone, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2,2′,4,4 ′-One or a mixture of two or more tetrahydroxybenzophenones.
对上述技术方案的进一步改进为，所述增粘剂为3‐氨基丙基三乙氧基硅烷、4‐氨基丁基三乙氧基硅烷、乙烯基三(β‐甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷中的一种。A further improvement to the above technical solution is that the tackifier is 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, vinyltris(β-methoxyethoxy) One of the silane and vinyltriethoxysilane.
一种自修复TPU热熔胶膜的制备方法，包括如下步骤：A method for preparing a self-healing TPU hot melt adhesive film, including the following steps:
S1、将配方量的原料加入到高速混合机中预混合，得到熔融料；S1. Add the formula amount of raw materials into a high-speed mixer and premix to obtain molten material;
S2、将S1步骤得到的熔融料加入到双螺杆挤出机中挤出，得到热熔胶粒；S2. Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets;
S3、将S2步骤所得的热熔胶粒加入到流延机中流延得到热熔胶膜，流延温度为120‐140℃。S3. Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film. The casting temperature is 120-140°C.
对上述技术方案的进一步改进为，在所述S1步骤中，熔融温度为135‐150℃，搅拌速度为150‐200r/min，搅拌时间为5‐8分钟。A further improvement to the above technical solution is that in the S1 step, the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5-8 minutes.
对上述技术方案的进一步改进为，在所述S2步骤中，挤出温度为150‐170℃，搅拌速度为660‐850r/min。A further improvement to the above technical solution is that in the S2 step, the extrusion temperature is 150-170°C and the stirring speed is 660-850r/min.
有益效果beneficial effects
本发明采用自修复超分子化合物引入TPU聚合物分子链上，由于烯烃酰胺的聚硅氧烷或聚倍半硅氧烷单体自聚作用，在TPU聚合物中形成了氢键交联网络，通过氢键的断裂与愈合，赋予材料具有良好的自修复能力，赋予材料可重复加工、可主动自修复等特殊性能，从而降低了在线修复操作的繁琐性，而且降低了修复成本，提升了产品的使用寿命及效率。The present invention uses self-repairing supramolecular compounds to introduce into the TPU polymer molecular chain. Due to the self-polymerization of polysiloxane or polysilsesquioxane monomers of olefin amide, a hydrogen bond cross-linked network is formed in the TPU polymer. Through the breaking and healing of hydrogen bonds, the material has good self-healing ability and special properties such as repeatable processing and active self-healing, thereby reducing the tediousness of online repair operations, reducing repair costs, and improving products. service life and efficiency.
本发明的实施方式Embodiments of the invention
下面结合具体实施方式，对本发明做进一步描述，需要说明的是，在不相冲突的前提下，以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。The present invention will be further described below in conjunction with specific implementation modes. It should be noted that, provided there is no conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.
一种自修复TPU热熔胶膜，包括如下重量份的原料：TPU颗粒80‐100份；丁腈橡胶20‐43份；自修复超分子化合物5‐8份；交联剂2‐4份；紫外光稳定剂1‐2份；增粘剂0.5‐2份。A self-healing TPU hot-melt adhesive film includes the following raw materials in parts by weight: 80-100 parts of TPU particles; 20-43 parts of nitrile rubber; 5-8 parts of self-healing supramolecular compounds; 2-4 parts of cross-linking agent; 1-2 parts of UV stabilizer; 0.5-2 parts of tackifier.
进一步地，所述TPU颗粒的熔融流动指数为0.5‐40g/10min。Further, the melt flow index of the TPU particles is 0.5-40g/10min.
进一步地，所述丁腈橡胶为未经特殊处理的丁腈橡胶、氢化丁腈橡胶或羧基丁腈橡胶中的一种或多种的混合物。Further, the nitrile rubber is a mixture of one or more of nitrile rubber, hydrogenated nitrile rubber or carboxyl nitrile rubber without special treatment.
进一步地，所述自修复超分子化合物为含烯烃酰胺的聚硅氧烷或聚倍半硅氧烷单体的自聚物。Further, the self-healing supramolecular compound is an olefin amide-containing polysiloxane or a self-polymer of a polysilsesquioxane monomer.
自修复超分子化合物的制备方法包括如下步骤：室温搅拌条件下，将带有活性氨基结构的聚硅氧烷或聚倍半硅氧烷溶于二氯甲烷溶液中，依次加入烯烃酰氯基类化合物、活化剂，室温下合成反应10‐20h，其中氨基结构的聚硅氧烷或聚倍半硅氧烷与烯烃酰氯基类化合物的摩尔比为10:11‐15，活化剂与烯烃酰氯基类化合物的质量比为1:5‐10，合成反应结束后，将物料加入0.1‐1mol/L氢氧化钠溶液中碱洗，再加入0.5‐1mol/L稀盐酸溶液中酸洗及0.5‐1mol/L氯化镁溶液中盐洗，然后分层、有机相经干燥、去除溶剂后得到自修复超分子化合物。The preparation method of self-healing supramolecular compounds includes the following steps: under room temperature stirring conditions, dissolve polysiloxane or polysilsesquioxane with an active amino structure in a methylene chloride solution, and add olefin acyl chloride compounds in sequence , Activator, synthesis reaction at room temperature for 10-20 hours, in which the molar ratio of amino-structured polysiloxane or polysilsesquioxane to olefin acyl chloride-based compounds is 10:11-15, and the activator and olefin acyl chloride-based compounds are The mass ratio of the compounds is 1:5-10. After the synthesis reaction is completed, the material is added to 0.1-1mol/L sodium hydroxide solution for alkaline washing, and then added to 0.5-1mol/L dilute hydrochloric acid solution for acid washing and 0.5-1mol/L. L magnesium chloride solution is washed with salt, then separated into layers, the organic phase is dried, and the solvent is removed to obtain a self-healing supramolecular compound.
进一步地，所述交联剂为苯甲酸叔戊酯、叔丁基过氧化苯甲酸酯、过氧化苯甲酸叔戊酯、正丁基‐4，4‐二(叔丁基过氧化)戊酸酯、乙基‐3，3‐二(叔丁基过氧化)丁酸酯中的一种或几种的混合物。Further, the cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-butyl-4,4-di(tert-butylperoxy)pentyl One or a mixture of acid esters and ethyl-3,3-di(tert-butyl peroxy)butyrate.
进一步地，所述紫外光稳定剂为2‐羟基‐5‐氯二苯甲酮、2，2′‐四亚甲基双(3，1‐苯并噁嗪‐4‐酮)、2‐羟基‐4‐苯甲酰基氧基二苯甲酮、2‐(2‐羟基‐3，5‐二叔戊基苯基)苯并三唑、2，2′，4，4′‐四羟基二苯甲酮的一种或者两种以上的混合物。Further, the UV light stabilizer is 2-hydroxy-5-chlorobenzophenone, 2,2′-tetramethylene bis(3,1-benzoxazin-4-one), 2-hydroxy ‐4‐benzoyloxybenzophenone, 2‐(2‐hydroxy‐3,5‐di‐tert‐pentylphenyl)benzotriazole, 2,2′,4,4′‐tetrahydroxydiphenyl One or a mixture of two or more ketones.
进一步地，所述增粘剂为3‐氨基丙基三乙氧基硅烷、4‐氨基丁基三乙氧基硅烷、乙烯基三(β‐甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷中的一种。Further, the tackifier is 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane One of the oxysilanes.
一种自修复TPU热熔胶膜的制备方法，包括如下步骤：A method for preparing a self-healing TPU hot melt adhesive film, including the following steps:
S1、将配方量的原料加入到高速混合机中预混合，得到熔融料；S1. Add the formula amount of raw materials into a high-speed mixer and premix to obtain molten material;
S2、将S1步骤得到的熔融料加入到双螺杆挤出机中挤出，得到热熔胶粒；S2. Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets;
S3、将S2步骤所得的热熔胶粒加入到流延机中流延得到热熔胶膜，流延温度为120‐140℃。S3. Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film. The casting temperature is 120-140°C.
进一步地，在所述S1步骤中，熔融温度为135‐150℃，搅拌速度为150‐200r/min，搅拌时间为5‐8分钟。Further, in the S1 step, the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5-8 minutes.
进一步地，在所述S2步骤中，挤出温度为150‐170℃，搅拌速度为660‐850r/min。Further, in the S2 step, the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min.
实施例1Example 1
一种自修复TPU热熔胶膜的制备方法，包括如下步骤：A method for preparing a self-healing TPU hot melt adhesive film, including the following steps:
S1、将：TPU颗粒80份，丁腈橡胶20份，自修复超分子化合物5份，交联剂2份，紫外光稳定剂1份，增粘剂0.5份加入到高速混合机中预混合，得到熔融料；熔融温度为135‐150℃，搅拌速度为150‐200r/min，搅拌时间为5‐8分钟；S1. Add: 80 parts of TPU particles, 20 parts of nitrile rubber, 5 parts of self-healing supramolecular compounds, 2 parts of cross-linking agent, 1 part of UV stabilizer, and 0.5 parts of tackifier into a high-speed mixer to premix. Obtain molten material; the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5-8 minutes;
S2、将S1步骤得到的熔融料加入到双螺杆挤出机中挤出，得到热熔胶粒；挤出温度为150‐170℃，搅拌速度为660‐850r/min；S2. Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets; the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min;
S3、将S2步骤所得的热熔胶粒加入到流延机中流延得到热熔胶膜，流延温度为120‐140℃。S3. Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film. The casting temperature is 120-140°C.
实施例2Example 2
一种自修复TPU热熔胶膜的制备方法，包括如下步骤：A method for preparing a self-healing TPU hot melt adhesive film, including the following steps:
S1、将：TPU颗粒90份，丁腈橡胶25份，自修复超分子化合物6份，交联剂2份，紫外光稳定剂1.5份，增粘剂1份加入到高速混合机中预混合，得到熔融料；熔融温度为135‐150℃，搅拌速度为150‐200r/min，搅拌时间为5‐8分钟；S1. Add: 90 parts of TPU particles, 25 parts of nitrile rubber, 6 parts of self-healing supramolecular compounds, 2 parts of cross-linking agent, 1.5 parts of UV stabilizer, and 1 part of tackifier into a high-speed mixer to premix. Obtain molten material; the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5-8 minutes;
S2、将S1步骤得到的熔融料加入到双螺杆挤出机中挤出，得到热熔胶粒；挤出温度为150‐170℃，搅拌速度为660‐850r/min；S2. Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets; the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min;
S3、将S2步骤所得的热熔胶粒加入到流延机中流延得到热熔胶膜，流延温度为120‐140℃。S3. Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film. The casting temperature is 120-140°C.
实施例3Example 3
一种自修复TPU热熔胶膜的制备方法，包括如下步骤：A method for preparing a self-healing TPU hot melt adhesive film, including the following steps:
S1、将：TPU颗粒100份，丁腈橡胶43份，自修复超分子化合物8份，交联剂4份，紫外光稳定剂2份，增粘剂2份加入到高速混合机中预混合，得到熔融料；熔融温度为135‐150℃，搅拌速度为150‐200r/min，搅拌时间为5‐8分钟；S1. Add: 100 parts of TPU particles, 43 parts of nitrile rubber, 8 parts of self-healing supramolecular compounds, 4 parts of cross-linking agent, 2 parts of UV stabilizer, and 2 parts of tackifier into a high-speed mixer to premix. Obtain molten material; the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5-8 minutes;
S2、将S1步骤得到的熔融料加入到双螺杆挤出机中挤出，得到热熔胶粒；挤出温度为150‐170℃，搅拌速度为660‐850r/min；S2. Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets; the extrusion temperature is 150-170°C, and the stirring speed is 660-850r/min;
S3、将S2步骤所得的热熔胶粒加入到流延机中流延得到热熔胶膜，流延温度为120‐140℃。S3. Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film. The casting temperature is 120-140°C.
对比例1Comparative example 1
按照指定的各组分份数重复实施例1的制备方法，但不添加使用自修复超分子化合物。Repeat the preparation method of Example 1 according to the specified proportions of each component, but do not add or use the self-healing supramolecular compound.
对比例2Comparative example 2
按照指定的各组分份数重复实施例2的制备方法，但不添加使用自修复超分子化合物。Repeat the preparation method of Example 2 according to the specified proportions of each component, but do not add or use the self-healing supramolecular compound.
对比例3Comparative example 3
按照指定的各组分份数重复实施例3的制备方法，但不添加使用自修复超分子化合物。Repeat the preparation method of Example 3 according to the specified proportions of each component, but do not add or use the self-healing supramolecular compound.
实施例中热熔胶膜的性能如表1所示，其中自修复能力采用刀割划伤后自愈合能力和弯折后变形的恢复能力，自修复能力为划伤或变形后的胶膜经光照或加热自修复后的拉伸强度/胶膜初始拉伸强度×100％。The properties of the hot melt adhesive film in the embodiment are shown in Table 1, in which the self-healing ability refers to the self-healing ability after being scratched by a knife and the recovery ability after deformation after bending. The self-healing ability is the adhesive film after being scratched or deformed. Tensile strength after self-healing by light or heating/initial tensile strength of the film × 100%.
表1Table 1
Figure PCTCN2022112221-appb-000001
Figure PCTCN2022112221-appb-000001
以上对本发明创造的实施例进行了详细说明，但所述内容仅为本发明创造的较佳实施例，不能被认为用于限定本发明创造的实施范围。凡依本发明创造申请范围所作的均等变化与改进等，均归属于本发明创造的专利涵盖范围之内。The embodiments of the present invention have been described in detail above, but the contents described are only preferred embodiments of the present invention and cannot be considered to limit the implementation scope of the present invention. All equivalent changes and improvements made in accordance with the application scope of this invention shall fall within the scope of the patent covered by this invention.

Claims (10)

  1. 一种自修复TPU热熔胶膜，其特征在于，包括如下重量份的原料：TPU颗粒80‐100份；丁腈橡胶20‐43份；自修复超分子化合物5‐8份；交联剂2‐4份；紫外光稳定剂1‐2份；增粘剂0.5‐2份。A self-healing TPU hot-melt adhesive film, characterized by including the following raw materials in parts by weight: 80-100 parts of TPU particles; 20-43 parts of nitrile rubber; 5-8 parts of self-healing supramolecular compounds; cross-linking agent 2 -4 parts; 1-2 parts of UV stabilizer; 0.5-2 parts of tackifier.
  2. 根据权利要求1所述的自修复TPU热熔胶膜，其特征在于，所述TPU颗粒的熔融流动指数为0.5‐40g/10min。The self-healing TPU hot melt adhesive film according to claim 1, wherein the melt flow index of the TPU particles is 0.5-40g/10min.
  3. 根据权利要求1所述的自修复TPU热熔胶膜，其特征在于，所述丁腈橡胶为未经特殊处理的丁腈橡胶、氢化丁腈橡胶或羧基丁腈橡胶中的一种或多种的混合物。The self-healing TPU hot melt adhesive film according to claim 1, characterized in that the nitrile rubber is one or more of nitrile rubber, hydrogenated nitrile rubber or carboxyl nitrile rubber without special treatment. mixture.
  4. 根据权利要求1所述的自修复TPU热熔胶膜，其特征在于，所述自修复超分子化合物为含烯烃酰胺的聚硅氧烷或聚倍半硅氧烷单体的自聚物。The self-healing TPU hot melt adhesive film according to claim 1, wherein the self-healing supramolecular compound is an olefin amide-containing polysiloxane or a self-polymer of polysilsesquioxane monomer.
  5. 根据权利要求1所述的自修复TPU热熔胶膜，其特征在于，所述交联剂为苯甲酸叔戊酯、叔丁基过氧化苯甲酸酯、过氧化苯甲酸叔戊酯、正丁基‐4，4‐二(叔丁基过氧化)戊酸酯、乙基‐3，3‐二(叔丁基过氧化)丁酸酯中的一种或几种的混合物。The self-healing TPU hot melt adhesive film according to claim 1, characterized in that the cross-linking agent is tert-amyl benzoate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, n-amyl peroxybenzoate, One or a mixture of butyl-4,4-di(tert-butylperoxy)valerate and ethyl-3,3-di(tert-butylperoxy)butyrate.
  6. 根据权利要求1所述的自修复TPU热熔胶膜，其特征在于，所述紫外光稳定剂为2‐羟基‐5‐氯二苯甲酮、2，2′‐四亚甲基双(3，1‐苯并噁嗪‐4‐酮)、2‐羟基‐4‐苯甲酰基氧基二苯甲酮、2‐(2‐羟基‐3，5‐二叔戊基苯基)苯并三唑、2，2′，4，4′‐四羟基二苯甲酮的一种或者两种以上的混合物。The self-healing TPU hot melt adhesive film according to claim 1, characterized in that the ultraviolet light stabilizer is 2-hydroxy-5-chlorobenzophenone, 2,2′-tetramethylene bis(3 , 1-benzoxazine-4-one), 2-hydroxy-4-benzoyloxybenzophenone, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotrizoate One or a mixture of two or more azoles, 2,2′,4,4′-tetrahydroxybenzophenones.
  7. 根据权利要求1所述的自修复TPU热熔胶膜，其特征在于，所述增粘剂为3‐氨基丙基三乙氧基硅烷、4‐氨基丁基三乙氧基硅烷、乙烯基三(β‐甲氧基乙氧基)硅烷、乙烯基三乙氧基硅烷中的一种。The self-healing TPU hot melt adhesive film according to claim 1, characterized in that the tackifier is 3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, vinyltriethoxysilane One of (β-methoxyethoxy)silane and vinyltriethoxysilane.
  8. 一种自修复TPU热熔胶膜的制备方法，其特征在于，包括如下步骤：A method for preparing a self-healing TPU hot melt adhesive film, which is characterized by including the following steps:
    S1、将配方量的原料加入到高速混合机中预混合，得到熔融料；S1. Add the formula amount of raw materials into a high-speed mixer and premix to obtain molten material;
    S2、将S1步骤得到的熔融料加入到双螺杆挤出机中挤出，得到热熔胶粒；S2. Add the molten material obtained in step S1 to a twin-screw extruder for extrusion to obtain hot melt rubber pellets;
    S3、将S2步骤所得的热熔胶粒加入到流延机中流延得到热熔胶膜，流延温度为120‐140℃。S3. Add the hot melt adhesive particles obtained in step S2 to a casting machine and cast them to obtain a hot melt adhesive film. The casting temperature is 120-140°C.
  9. 根据权利要求8所述的自修复TPU热熔胶膜的制备方法，其特征在于，在所述S1步骤中，熔融温度为135‐150℃，搅拌速度为150‐200r/min，搅拌时间为5‐8分钟。The method for preparing a self-healing TPU hot melt adhesive film according to claim 8, characterized in that in the step S1, the melting temperature is 135-150°C, the stirring speed is 150-200r/min, and the stirring time is 5 -8 minutes.
  10. 根据权利要求8所述的自修复TPU热熔胶膜的制备方法，其特征在于，在所述S2步骤中，挤出温度为150‐170℃，搅拌速度为660‐850r/min。The method for preparing a self-healing TPU hot melt adhesive film according to claim 8, characterized in that in the step S2, the extrusion temperature is 150-170°C and the stirring speed is 660-850r/min.
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