WO2023184663A1 - 一种耐高温水洗tpu热熔胶膜及其制备方法 - Google Patents

一种耐高温水洗tpu热熔胶膜及其制备方法 Download PDF

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WO2023184663A1
WO2023184663A1 PCT/CN2022/092779 CN2022092779W WO2023184663A1 WO 2023184663 A1 WO2023184663 A1 WO 2023184663A1 CN 2022092779 W CN2022092779 W CN 2022092779W WO 2023184663 A1 WO2023184663 A1 WO 2023184663A1
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temperature
melt adhesive
adhesive film
tpu
washable
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PCT/CN2022/092779
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French (fr)
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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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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2481/06—Polysulfones; Polyethersulfones

Definitions

  • the invention relates to the field of hot-melt adhesive films, and in particular to a high-temperature water-washable TPU hot-melt adhesive film and a preparation method thereof.
  • TPU hot melt adhesive film is a common hot melt adhesive product used in daily life and industrial production. It is solid and non-sticky at room temperature and will melt at high temperatures. It is sticky on both sides and is an environmentally friendly adhesive. It has high tensile strength, excellent flexibility, weather resistance, transparency, comfortable contact with the human body, easy processing, and high bonding strength with various materials. It is widely used in the bonding of various materials such as jackets, sports fabrics, trademark woven labels, embroidery, heat transfer and textiles. TPU hot melt adhesive film needs to have excellent water resistance. After the fabric is bonded with the hot melt adhesive film, it can maintain a high bonding strength after being soaked in water at a certain temperature and repeatedly rubbed.
  • the existing TPU hot-melt adhesive film has certain room-temperature water-washing resistance, but its high-temperature water-washing resistance is poor, which limits its application fields.
  • the present invention provides a high temperature resistant water-washable TPU hot melt adhesive film with high tensile strength and weather resistance.
  • the invention also provides a method for preparing a high-temperature water-washable TPU hot-melt adhesive film, which has a simple process and is easy to operate.
  • a high-temperature washable TPU hot-melt adhesive film includes the following raw materials by weight:
  • TPU particles are one of polycarbonate polyester TPU particles and polytetrahydrofuran polyether TPU particles.
  • a further improvement to the above technical solution is that the hardness of the TPU particles is 90-95A.
  • modified polyester is one or both of modified copolyester 3112 and modified copolyester 5120.
  • hydrolysis-resistant auxiliary agent is one or more of maleic anhydride-grafted PE, phenyl glycidyl ether, and bisphenol A diglycidyl ether.
  • a further improvement to the above technical solution is that when the modified polyester is modified copolyester 3112 and modified copolyester 5120, the mass ratio of modified copolyester 3112 and modified copolyester 5120 is 1- 2:1-2.
  • tackifier is any one of phenolic resin, terpene-phenolic resin, terpene phenol resin or a mixture of at least two of them.
  • the inorganic filler is any one or a mixture of at least two of talc powder, mica powder, titanium dioxide, white carbon black, and carbon black.
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • a further improvement to the above technical solution is that the screw of the twin-screw extruder has five temperature zones, respectively, the temperature of barrel 1 is 155-165°C, the temperature of barrel 2 is 180-190°C, and the temperature of barrel 3 is 180-190°C. 190°C, the temperature of barrel 4 is 180 ⁇ 190°C, and the temperature of barrel 5 is 180 ⁇ 190°C.
  • the synthesized TPU hot-melt adhesive film has a melting point of 95-120°C, is high temperature resistant, and can maintain high bonding strength after being soaked in water of a certain temperature and repeatedly rubbed; using modification
  • the modification of polyester and tackifier overcomes some shortcomings of a single material and achieves complementary advantages, so that the product has good bonding performance. After high-temperature water washing, the bonding strength retention rate is more than 93%, and no glue is opened; using Polyethersulfone powder has higher heat resistance and rigidity, further improving the heat resistance of the product.
  • a high-temperature washable TPU hot-melt adhesive film includes the following raw materials by weight:
  • the TPU particles are one of polycarbonate-based polyester TPU particles and polytetrahydrofuran-based polyether TPU particles; the hardness of the TPU particles is 90-95A.
  • modified polyester is one or both of modified copolyester 3112 and modified copolyester 5120.
  • the hydrolysis resistance auxiliary is one or more of maleic anhydride-grafted PE, phenyl glycidyl ether, and bisphenol A diglycidyl ether.
  • the mass ratio of modified copolyester 3112 and modified copolyester 5120 is 1-2:1-2.
  • the tackifier is any one of phenolic resin, terpene-phenolic resin, terpene-phenol resin or a mixture of at least two.
  • the inorganic filler is any one or a mixture of at least two of talc powder, mica powder, titanium dioxide, white carbon black, and carbon black.
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • the screw of the twin-screw extruder has five temperature zones, respectively, the temperature of barrel 1 is 155-165°C, the temperature of barrel 2 is 180-190°C, the temperature of barrel 3 is 180-190°C, and the temperature of barrel 4 is 180-190°C. The temperature is 180 ⁇ 190°C, and the temperature of barrel 5 is 180 ⁇ 190°C.
  • a high-temperature washable TPU hot-melt adhesive film includes the following raw materials by weight:
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • a high-temperature washable TPU hot-melt adhesive film includes the following raw materials by weight:
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • a high-temperature washable TPU hot-melt adhesive film includes the following raw materials by weight:
  • Polytetrahydrofuran polyether type TPU particles 95 copies Modified copolyester 3112 30 servings Bisphenol A diglycidyl ether 10 servings Polyethersulfone powder 10 servings Phenolic Resin 1 serving talcum powder 0.5 servings
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • TPU hot melt adhesive film includes the following raw materials by weight:
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • TPU hot melt adhesive film includes the following raw materials by weight:
  • TPU particles 90 copies Polyethersulfone powder 10 servings Phenolic Resin 1 serving talcum powder 0.5 servings
  • a method for preparing a high-temperature water-resistant TPU hot-melt adhesive film including the following steps:
  • the TPU hot melt adhesive film materials of Examples 1-3 and Comparative Examples 1-2 were tested for performance.
  • the test methods were as follows: the melting point test was performed using differential scanning calorimetry (DSC); the tensile strength test was performed according to GB/T 528- 2009 standard; bonding strength test follows GB/T2792-2014 standard; water washability test: tested in accordance with ISO 6330 standard, washed 20 times in water at a temperature of 50 or 60°C, 60 minutes each time; peel strength: 20cm wide adhesive film Press the elastic fabric at 150°C for 15 seconds, and after cooling for 60 minutes, test its peel strength.
  • the results are shown in Table 1 below.
  • the present invention enables the properties of different materials to complement each other, and the products obtained have the characteristics of good bonding performance, excellent water resistance, good tensile strength, bonding strength and peel strength.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明涉及热熔胶膜领域，特别是涉及一种耐高温水洗TPU热熔胶膜，包括如下重量份的原料：TPU颗粒85-100份；改性聚酯18-30份；耐水解助剂5-20份；聚醚砜粉末3-10份；增粘剂0.1-1份；无机填料0.1-0.5份。本发明提供具有很高的抗拉强度、耐候性的一种耐高温水洗TPU热熔胶膜；本发明还提供一种耐高温水洗TPU热熔胶膜的制备方法，工艺简单，操作简便。

Description

一种耐高温水洗TPU热熔胶膜及其制备方法 技术领域
本发明涉及热熔胶膜领域，特别是涉及一种耐高温水洗TPU热熔胶膜及其制备方法。
背景技术
TPU热熔胶膜是一种应用到生活及工业生产常见的热熔胶产品，常温状态为固态没有粘性，高温状态会熔化，双面具有粘性，属于环保型胶粘剂。具有很高的抗拉强度、极佳的柔软弯曲性、耐候性、透明性，与人体接触舒适、易加工，与各种材质粘合强度高。广泛应用于冲锋衣，运动面料，商标织唛，绣花，烫画以及纺织品等各类材料的粘接。TPU热熔胶膜需要具有优良的耐水洗性能，面料经过热熔胶膜粘接后，经过一定温度的水浸泡和反复揉搓，还能保持较高的粘接强度。
现有TPU热熔胶膜具备一定的常温耐水洗性能，但耐高温水洗性能较差，限制了应用领域。
发明内容
为解决上述技术问题，本发明提供具有很高的抗拉强度、耐候性的一种耐高温水洗TPU热熔胶膜。
本发明还提供一种耐高温水洗TPU热熔胶膜的制备方法，工艺简单，操作简便。
本发明采用如下技术方案：
一种耐高温水洗TPU热熔胶膜，包括如下重量份的原料：
Figure PCTCN2022092779-appb-000001
Figure PCTCN2022092779-appb-000002
对上述技术方案的进一步改进为，所述TPU颗粒为聚碳酸酯系聚酯型TPU颗粒、聚四氢呋喃系聚醚型TPU颗粒中的一种。
对上述技术方案的进一步改进为，所述TPU颗粒的硬度为90-95A。
对上述技术方案的进一步改进为，所述改性聚酯为改性共聚酯3112、改性共聚酯5120中的一种或两种。
对上述技术方案的进一步改进为，所述耐水解助剂为马来酸酐接枝PE、苯基缩水甘油醚、双酚A双缩水甘油醚中的一种或多种。
对上述技术方案的进一步改进为，所述改性聚酯为改性共聚酯3112、改性共聚酯5120时，改性共聚酯3112、改性共聚酯5120的质量比为1-2：1-2。
对上述技术方案的进一步改进为，所述增粘剂为酚醛树脂、萜烯-酚醛树脂、萜烯酚树脂中的任意一种或者至少两种的混合物。
对上述技术方案的进一步改进为，所述无机填料为滑石粉、云母粉、二氧化钛、白炭黑、炭黑中的任意一种或者至少两种的混合物。
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述的重量份配方，混合机混配2.5-4h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得耐高温水洗TPU热熔胶膜。
对上述技术方案的进一步改进为，所述双螺杆挤出机的螺杆具有五段温度区，分别为料筒1温度155～165℃，料筒2温度180～190℃，料筒3温度180～190℃，料筒4温度180～190℃，料筒5温度180～190℃。
本发明的有益效果为：
本发明通过配方控制，合成的TPU热熔胶膜熔点在95-120℃，耐高温，经过一定温度的水的浸泡和反复揉搓后，还能保持较高的粘接强度的性能；采用改性聚酯、增粘剂的改性，克服了单一材料的一些缺点，达到优势互补，从而使产品具有良好的粘接性能，经过高温水洗，粘接强度保持率在93％以上，不 开胶；采用聚醚砜粉末，其有更高的耐热性与刚性，进一步提高产品的耐热性能。
具体实施方式
现在结合具体实施例对本发明作进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
一种耐高温水洗TPU热熔胶膜，包括如下重量份的原料：
Figure PCTCN2022092779-appb-000003
进一步地，所述TPU颗粒为聚碳酸酯系聚酯型TPU颗粒、聚四氢呋喃系聚醚型TPU颗粒中的一种；所述TPU颗粒的硬度为90-95A。
进一步地，所述改性聚酯为改性共聚酯3112、改性共聚酯5120中的一种或两种。
进一步地，所述耐水解助剂为马来酸酐接枝PE、苯基缩水甘油醚、双酚A双缩水甘油醚中的一种或多种。
进一步地，所述改性聚酯为改性共聚酯3112、改性共聚酯5120时，改性共聚酯3112、改性共聚酯5120的质量比为1-2：1-2。
进一步地，所述增粘剂为酚醛树脂、萜烯-酚醛树脂、萜烯酚树脂中的任意一种或者至少两种的混合物。
进一步地，所述无机填料为滑石粉、云母粉、二氧化钛、白炭黑、炭黑中的任意一种或者至少两种的混合物。
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述重量份配方，混合机混配2.5-4h，混合均匀后，用双螺杆挤出机流 延成型或吹膜成型，制得耐高温水洗TPU热熔胶膜。
进一步地，所述双螺杆挤出机的螺杆具有五段温度区，分别为料筒1温度155～165℃，料筒2温度180～190℃，料筒3温度180～190℃，料筒4温度180～190℃，料筒5温度180～190℃。
实施例1
一种耐高温水洗TPU热熔胶膜，包括如下重量份的原料：
聚碳酸酯系聚酯型TPU颗粒 85份
改性共聚酯3112 20份
苯基缩水甘油醚 5份
聚醚砜粉末 3份
酚醛树脂 1份
滑石粉 0.5份
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述重量份配方，混合机混配2.5h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得耐高温水洗TPU热熔胶膜。
实施例2
一种耐高温水洗TPU热熔胶膜，包括如下重量份的原料：
聚碳酸酯系聚酯型TPU颗粒 90份
改性共聚酯5120 18份
马来酸酐接枝PE 10份
聚醚砜粉末 5份
酚醛树脂 1份
滑石粉 0.5份
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述重量份配方，混合机混配3h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得耐高温水洗TPU热熔胶膜。
实施例3
一种耐高温水洗TPU热熔胶膜，包括如下重量份的原料：
聚四氢呋喃系聚醚型TPU颗粒 95份
改性共聚酯3112 30份
双酚A双缩水甘油醚 10份
聚醚砜粉末 10份
酚醛树脂 1份
滑石粉 0.5份
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述重量份配方，混合机混配4h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得耐高温水洗TPU热熔胶膜。
对比例1
TPU热熔胶膜包括如下重量份的原料：
TPU颗粒 85份
聚醚砜粉末 3份
酚醛树脂 1份
滑石粉 0.5份
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述重量份配方，混合机混配2.5h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得TPU热熔胶膜。
对比例2
TPU热熔胶膜包括如下重量份的原料：
TPU颗粒 90份
聚醚砜粉末 10份
酚醛树脂 1份
滑石粉 0.5份
一种耐高温水洗TPU热熔胶膜的制备方法，包括如下步骤：
采用上述重量份配方，混合机混配2.5h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得TPU热熔胶膜。
将实施例1-3和对比例1-2的TPU热熔胶膜材料进行性能测试，测试方法如下：熔点测试采用示差扫描量热法(DSC)测试；拉伸强度测试执行GB/T 528-2009标准；粘接强度测试执行GB/T2792-2014标准；水洗性测试：按照ISO 6330标准测试，温度为50或60℃中水洗20次，每次60分钟；剥离强度：将20cm宽的胶膜于150℃下压弹力面料15S，冷却60分钟后，检测其剥离强度，结果如下表1所示。
表1
Figure PCTCN2022092779-appb-000004
由表中可知，本发明使不同材料的性能达到优势互补，获得的产品具有良好的粘接性能、优异的耐水性、良好的拉伸强度、粘接强度及剥离强度等特点。
本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，上述实施例说明本发明的详细方法，但本发明并不局限于上面揭示和描述的具体实施方式，也不意味着本发明必须依赖上述详细方法才能实施，对发明的一些修改和变更等任何改进，对本发明产品各原料的等效替换及辅助成分的添加，具体方式的选择等，也应当落入本发明的权利要求的保护范围内。

Claims (10)

  1. 一种耐高温水洗TPU热熔胶膜，其特征在于，包括如下重量份的原料：
    Figure PCTCN2022092779-appb-100001
  2. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述TPU颗粒为聚碳酸酯系聚酯型TPU颗粒、聚四氢呋喃系聚醚型TPU颗粒中的一种。
  3. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述TPU颗粒的硬度为90-95A。
  4. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述改性聚酯为改性共聚酯3112、改性共聚酯5120中的一种或两种。
  5. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述耐水解助剂为马来酸酐接枝PE、苯基缩水甘油醚、双酚A双缩水甘油醚中的一种或多种。
  6. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述改性聚酯为改性共聚酯3112、改性共聚酯5120时，改性共聚酯3112、改性共聚酯5120的质量比为1-2：1-2。
  7. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述增粘剂为酚醛树脂、萜烯-酚醛树脂、萜烯酚树脂中的任意一种或者至少两种的混合物。
  8. 根据权利要求1所述的耐高温水洗TPU热熔胶膜，其特征在于，所述无机填料为滑石粉、云母粉、二氧化钛、白炭黑、炭黑中的任意一种或者至少两种的混合物。
  9. 一种耐高温水洗TPU热熔胶膜的制备方法，其特征在于，包括如下步骤：
    采用如权利要求1-8任一项所述的重量份配方，混合机混配2.5-4h，混合均匀后，用双螺杆挤出机流延成型或吹膜成型，制得耐高温水洗TPU热熔胶膜。
  10. 根据权利要求9所述的耐高温水洗TPU热熔胶膜的制备方法，其特征在于，所述双螺杆挤出机的螺杆具有五段温度区，分别为料筒1温度155～165℃，料筒2温度180～190℃，料筒3温度180～190℃，料筒4温度180～190℃，料筒5温度180～190℃。
PCT/CN2022/092779 2022-03-29 2022-05-13 一种耐高温水洗tpu热熔胶膜及其制备方法 WO2023184663A1 (zh)

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