WO2017107859A1 - 一种新型热熔胶及其制备方法 - Google Patents

一种新型热熔胶及其制备方法 Download PDF

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WO2017107859A1
WO2017107859A1 PCT/CN2016/110282 CN2016110282W WO2017107859A1 WO 2017107859 A1 WO2017107859 A1 WO 2017107859A1 CN 2016110282 W CN2016110282 W CN 2016110282W WO 2017107859 A1 WO2017107859 A1 WO 2017107859A1
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melt adhesive
hot melt
nylon
novel hot
salt
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PCT/CN2016/110282
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English (en)
French (fr)
Inventor
曾作祥
马星全
李哲龙
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KUNSHAN TIANYANG HOT MELT ADHESIVE CO Ltd
SHANGHAI TIANYANG HOT MELT ADHESIVE CO Ltd
East China University of Science and Technology
Original Assignee
KUNSHAN TIANYANG HOT MELT ADHESIVE CO Ltd
SHANGHAI TIANYANG HOT MELT ADHESIVE CO Ltd
East China University of Science and Technology
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Application filed by KUNSHAN TIANYANG HOT MELT ADHESIVE CO Ltd, SHANGHAI TIANYANG HOT MELT ADHESIVE CO Ltd, East China University of Science and Technology filed Critical KUNSHAN TIANYANG HOT MELT ADHESIVE CO Ltd
Priority to DE112016005861.6T priority Critical patent/DE112016005861T5/de
Priority to CH00787/18A priority patent/CH713470B1/de
Priority to KR1020187020977A priority patent/KR102176466B1/ko
Priority to US16/064,235 priority patent/US10703938B2/en
Publication of WO2017107859A1 publication Critical patent/WO2017107859A1/zh
Anticipated expiration legal-status Critical
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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
    • 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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
    • C08L23/286—Chlorinated polyethylene
    • 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
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C09J2427/00—Presence of halogenated polymer
    • 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
    • C09J2451/00—Presence of graft polymer
    • 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
    • C09J2493/00—Presence of natural resin
    • 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
    • C09J2495/00—Presence of bitume

Definitions

  • the invention relates to a novel hot melt adhesive and a preparation method thereof, in particular to a hot melt adhesive for bonding or compounding metal materials such as aluminum and stainless steel with PVC plastic and a preparation method thereof.
  • Polyvinyl chloride is a widely used plastic.
  • the annual output of PVC in the world can reach 50 million tons.
  • the annual waste PVC is also 10 million tons. How to recycle them is not only an economic problem, but also It is an environmental protection issue.
  • the combination of waste PVC and metal sheet to form a plastic-steel composite material with metal as a panel has a wide range of uses. If the adhesive used for the composite bonding is an environmentally-friendly hot melt adhesive, the above two related to the waste PVC can be simultaneously solved. Big problems can not only bring great economic effects, but also have positive effects on environmental protection.
  • the composite of plastic and metal is mainly bonded directly by liquid glue such as epoxy glue and polyurethane glue, and the liquid glue contains volatile substances, which is easy to pollute the environment, and the processing operation is inconvenient.
  • liquid glue such as epoxy glue and polyurethane glue
  • the hot melt adhesive contains no solvent, has no pollution to the environment, and is convenient and quick to process, which is beneficial to the large-scale and fast operation of the factory.
  • Patent CN101792641A discloses an adhesive for aluminum alloy and PVC film which is a fast curing adhesive which, although shortening the drying solvent procedure, has a shorter storage time. Inconvenient for practical application; patent CN103059792B describes a polyester elastomer hot melt adhesive for bonding polar polymers and metal materials and a preparation method thereof, but the hot melt adhesive does not adhere to PVC. Strong, and its water resistance is poor; patent CN103756577A discloses a PVC/metal bonded hot melt adhesive film and a preparation method thereof, but the hot melt adhesive has short aging for metal adhesion and is easy to be degummed from metal.
  • the peel strength is poor;
  • the patent CN103045111B discloses a copolyester-based hot melt adhesive which can be used for bonding between a metal and a polar material, but which has obvious defects, as can be seen from the embodiment thereof,
  • the disclosed hot melt adhesive uses a temperature of 138 ° C, and The heat resistance of PVC is poor, and compounding at a temperature of 138 °C is likely to cause deformation of PVC.
  • the object of the present invention is to solve the above technical problems, and to provide a novel hot melt adhesive and a preparation method thereof, so that the novel hot melt adhesive prepared by the invention can meet the composite bonding requirements of metal and PVC plastic.
  • the technical scheme adopted by the invention is: a novel hot melt adhesive, the raw material composition thereof, including: nylon type copolyamide 63% to 70%, perchloroethylene resin 15% to 20%, tackifier 13% to 17%, silane coupling agent 0.3% to 1%, and plasticizer 0.5% to 1%.
  • the above nylon type copolyamide is composed of caprolactam, nylon 66 salt (i.e., hexamethylenediamine adipate), nylon 612 salt (i.e., hexamethylenediamine adipate), and nylon 1010 salt (i.e., decyl sebacate).
  • the main raw materials are copolymerized by an appropriate amount of water and stearic acid, and the molar percentages of the above four main raw materials are 33% to 40%, 32% to 38%, 15% to 20%, and 12% to 16%, respectively. %; and the molar ratio of the above stearic acid to caprolactam is 0.02:1 to 0.03:1.
  • the chlorine content of the above perchloroethylene resin is 61% to 65%;
  • the above tackifier is selected from the group consisting of rosin, terpene resin or hydrogenated petroleum resin;
  • the above silane coupling agent is selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltriethoxysilane or ⁇ -aminopropyltrimethoxy One of the silanes;
  • the above plasticizer is one of dioctyl adipate and dioctyl sebacate.
  • the preparation method of the above novel hot glue comprises the following steps:
  • the mixed material is added to a twin-screw extruder and melt-extruded at a temperature of 100-130 ° C to obtain a new hot melt adhesive.
  • the new hot melt adhesive can be made into a hot melt adhesive film according to actual needs, and the preparation steps are as follows: the new hot melt adhesive is coated by a casting machine or a hot melt coating device. The cloth can be made into a new hot melt adhesive film, and the new hot melt adhesive film has a thickness of 0.1 mm.
  • the method for preparing a nylon type copolyamide comprises the following steps:
  • the prepared nylon type copolyamide can be prepared according to actual needs, such as strip, granule or powder.
  • the amount of water added in the above step (2b) can be adjusted according to actual needs, as long as the ring-opening caprolactam can be hydrolyzed.
  • the invention is innovative in that a specific nylon-type copolyamide is prepared by designing a specific raw material and its ratio, and the good adhesion property to the metal is combined with the good adhesion property of the polyvinyl chloride resin to the PVC.
  • the twin-screw extruder Through the twin-screw extruder, the two are fully melt-blended under the synergistic action of related additives, and the obtained new hot melt adhesive has good bonding properties to both metal and PVC.
  • the novel hot-melt adhesive prepared by the invention can realize the rapid adhesion of metal and PVC plastic through a laminating machine or a pressing machine, and has a simple process and a bonding speed. Quick advantage.
  • the new hot melt adhesive prepared by the invention can be effectively bonded and composited at a temperature of about 80 ° C in practical use, and the application temperature is low, the operation is convenient, and the PVC material is not damaged.
  • nylon type copolyamide 90.44g of caprolactam, 199.35g of nylon 66 salt, 103.89g of nylon 612 salt and 97.32g of nylon 1010 salt were mixed and added to a 2L high pressure reactor with stirrer, thermometer and pressure gauge. Adding 4.836g of stearic acid and 70g of deionized water, replacing it with nitrogen and vacuuming, removing the air in the reaction vessel; then filling with 0.2MPa of high-purity nitrogen, heating slowly to 230 ° C, at 1.0- Under the pressure of 1.2 MPa, the reaction was kept for 3 hours, and the pressure was gradually reduced to normal pressure, and the pressure was further reduced to 0.05 MPa for 1 hour.
  • the pellets were pelletized to obtain a granulated nylon-type copolyamide (PA-1).
  • PA-1 granulated nylon-type copolyamide
  • the final melting point of DS-1 of PA-1 was 88 ° C
  • the melt flow rate was 48 g/10 min / 160 ° C / 2.16 kg.
  • nylon type copolyamide 106.4 g of caprolactam, 170.5 g of nylon 66 salt, 107.35 g of nylon 612 salt and 89.83 g of nylon 1010 salt were mixed and added to a 2 L high pressure reactor equipped with a stirrer, a thermometer and a pressure gauge.
  • nylon type copolyamide 87.78 g of caprolactam, 173.12 g of nylon 66 salt, 138.52 g of nylon 612 salt and 104.8 g of nylon 1010 salt were mixed and added to a 2 L high pressure reaction kettle equipped with a stirrer, a thermometer and a pressure gauge. Then add 5.633g of stearic acid and 60g of deionized water, replace with nitrogen and vacuum, remove the air in the reaction kettle; then fill with 0.2MPa high-purity nitrogen, heat slowly to 230 ° C, at 1.0- Under the pressure of 1.2 MPa, the reaction was kept for 3 hours, and the pressure was gradually reduced to normal pressure, and the pressure was further reduced to 0.05 MPa for 1 hour.
  • the pellet was discharged to obtain a granulated nylon-type copolyamide (PA-3).
  • PA-3 granulated nylon-type copolyamide
  • the final melting point of DS-3 of PA-3 was 85 ° C, and the melt flow rate was 43.8 g/10 min / 160 ° C / 2.16 kg.
  • a new hot melt adhesive 400g of nylon type copolyamide (PA-3), 89.71g of perchloroethylene resin, 74.29g of terpene resin, 1.71g of ⁇ -aminopropyltrimethoxysilane, and 5.81 of azelaic acid g, put into a high-speed mixer to mix evenly; then put the mixed material into the TE35 twin-screw extruder, Blending and melting; after discharging, casting and cooling to make a 0.10 mm hot melt adhesive film.
  • the film sample is labeled A3.
  • nylon type copolyamide 97.09 g of caprolactam, 167.87 g of nylon 66 salt, 107.35 g of nylon 612 salt and 119.78 g of nylon 1010 salt were mixed and added to a 2 L high pressure reaction kettle equipped with a stirrer, a thermometer and a pressure gauge.
  • the obtained film samples were bonded to 180° peel strength of PVC/aluminum and PVC/stainless steel at 80 ° C, 0.3 MPa, and hot pressed for 20 s.
  • the test method refers to GB/T 2790-1995, and the test results are shown in Table 1.
  • Table 1 shows the bond strength of the hot melt adhesive film obtained in each example to PVC/metal.
  • the new hot melt adhesive prepared by the present invention has better bonding strength properties to metal and PVC.
  • the pressing temperature is lower, 80 ° C, will not cause damage to the PVC material; the pressing time is also short, 20s, which is convenient for construction operation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明涉及一种新型热熔胶及其制备方法，特别是一种用于粘接或复合铝、不锈钢等金属材料与PVC塑料的热熔胶及其制备方法。其主要是通过设计特定原料及其配比，先行制备特定的尼龙型共聚酰胺，利用其对金属的良好粘接性能，再结合过氯乙烯树脂对PVC的良好粘接特性，通过双螺杆挤出机使得二者在相关助剂的协同作用下充分熔融共混，获得的新型热熔胶对金属和PVC均具有较好的粘接性能。

Description

一种新型热熔胶及其制备方法 技术领域
本发明涉及一种新型热熔胶及其制备方法，特别是一种用于粘接或复合铝、不锈钢等金属材料与PVC塑料的热熔胶及其制备方法。
背景技术
聚氯乙烯(PVC)是一种应用十分广泛的塑料，全球PVC年产量可达五千万吨级别，每年产生的废旧PVC也达千万吨级别，如何循环使用它们不仅是一个经济问题，更是一个环境保护问题。将废旧PVC与金属片复合、形成以金属为面板的塑钢复合材料，具有广泛的用途，如果复合粘接所用胶黏剂为环保型的热熔胶，将可同时解决与废旧PVC有关的上述两大问题，不仅能带来极大经济效应，而且对环境保护具有积极效果。
目前塑料与金属的复合主要是通过环氧胶、聚氨酯胶等液体胶直接粘结，而液体胶含有挥发性物质，容易污染环境，而且加工操作不方便。热熔胶不含溶剂，对环境无污染，加工操作方便快捷，有利于工厂大规模快速作业。
专利CN101792641A公布了一种用于铝合金和PVC膜的粘合剂，该粘合剂是一种快速固化的粘合剂，虽然缩短了烘干溶剂程序，但粘合剂的储存时间较短，给实际应用带来不便；专利CN103059792B介绍了一种用于粘结极性聚合物和金属材料的聚酯弹性体热熔胶及其制备方法，但这种热熔胶对PVC的粘结性不强，而且其耐水性较差；专利CN103756577A公布了一种PVC/金属粘结热熔胶膜及其制备方法，但是该热熔胶对于金属的粘结附着时效短，容易从金属上脱胶，总体的剥离强度较差；专利CN103045111B公开了一种基于共聚酯的热熔胶，可用于金属与极性材料之间的粘接，但其存在明显缺陷，从其实施例中可以看出，该发明所公开的热熔胶使用温度为138℃，而 PVC的耐热性较差，在温度138℃下复合很可能造成PVC变形。
综上所述，现有热熔胶对金属与PVC塑料的粘接性能还不能够满足实际应用方面的需求。开发一种新型热熔胶，专业用于粘接金属及PVC塑料，成为亟待解决的问题。
发明内容
本发明的目的在于解决上述技术问题，提供一种新型热熔胶及其制备方法，使得通过本发明制备得出的新型热熔胶，能够满足金属与PVC塑料的复合粘接要求。
本发明所采用的技术方案为：一种新型热熔胶，其原料构成，按质量百分比计，包括：尼龙型共聚酰胺63％～70％、过氯乙烯树脂15％～20％、增粘剂13％～17％、硅烷偶联剂0.3％～1％、增塑剂0.5％～1％。
上述尼龙型共聚酰胺由己内酰胺、尼龙66盐(即己二酸己二胺盐)、尼龙612盐(即己二酸己二胺盐)及尼龙1010盐(即癸二酸癸二胺盐)四种主要原料在适量的水和硬脂酸作用下共聚而成，且上述四种主要原料的摩尔百分比分别为33％～40％、32％～38％、15％～20％及12％～16％；而上述硬脂酸与己内酰胺的摩尔比为0.02:1～0.03:1。
上述过氯乙烯树脂的氯含量为61％～65％；
上述增粘剂选自松香、萜烯树脂或氢化石油树脂中的一种；
上述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、N-(β-氨基乙基)-γ-氨基丙基三乙氧基硅烷或γ-氨基丙基三甲氧基硅烷中的一种；
上述增塑剂为己二酸二辛酯和癸二酸二辛酯中的一种。
上述新型热胶的制备方法，包括如下步骤：
(1)参考上述新型热胶的原料构成，选取原料；
(2)制备尼龙型共聚酰胺；
(3)将所制备的尼龙型共聚酰胺与过氯乙烯树脂、增粘剂、硅烷偶联剂及增塑剂按预设配比加入到高速混合机中，搅拌均匀；
(4)混合后的物料加入到双螺杆挤出机中，在100-130℃的温度下熔融挤出，即得新型热熔胶。
上述步骤(4)后，还可依据实际需求，将该新型热熔胶制成热熔胶膜，制备步骤为：将上述新型热熔胶通过流延机流延或热熔涂布设备进行涂布，即可制成新型热熔胶膜，且该新型热熔胶膜的厚度为0.1mm。
上述步骤(2)中，制备尼龙型共聚酰胺的方法包括如下步骤：
(2a)将己内酰胺、尼龙66盐、尼龙612盐、尼龙1010盐按比例混合后，加入到高压反应釜中；
(2b)再向高压反应釜中加入硬脂酸及一定量的水，然后用氮气置换并抽真空，除尽反应釜中的空气；
(2c)然后充入高纯氮气，加热慢慢升温至230℃，在1.0～1.2MPa压力下，保温反应3h，然后慢慢减压至常压，并继续减压至0.05MPa脱水1h；
(2d)然后放料，即得本发明所需尼龙型共聚酰胺。
所制备的尼龙型共聚酰胺可依实际需求制备其型态，如条状、粒状或粉状等。
在制备尼龙型共聚酰胺的方法步骤中，上述步骤(2b)中所加入的水的量可依实际需求自行调整，只要能够水解开环己内酰胺即可。
本发明的创新之处在于，通过设计特定原料及其配比，先行制备特定的尼龙型共聚酰胺，利用其对金属的良好粘接性能，再结合过氯乙烯树脂对PVC的良好粘接特性，通过双螺杆挤出机使得二者在相关助剂的协同作用下充分熔融共混，获得的新型热熔胶对金属和PVC均具有较好的粘接性能。相对于 现有的溶剂型或反应型液体粘合剂，通过本发明制备所得的新型热熔胶可以通过层压机或压烫机设备实现金属与PVC塑料的快速粘合，具有工艺简单、粘合速度快的优点。同时，通过本发明所制备的新型热熔胶在实际使用时，80℃左右温度下即可有效粘接复合，应用温度较低，方便操作，且不会对PVC材料造成损害。
具体实施方式
下面通过实施例对本发明做进一步表述，但并不以此为限。
实施例1
制备尼龙型共聚酰胺：将己内酰胺90.44g、尼龙66盐199.35g、尼龙612盐103.89g和尼龙1010盐97.32g混合后，加入到一个带有搅拌器、温度表和压力表的2L高压反应釜中；再加入硬脂酸4.836g和去离子水70g，用氮气置换并抽真空，除尽反应釜中的空气；然后充入0.2MPa的高纯氮气，加热慢慢升温至230℃，在1.0-1.2MPa的压力下，保温反应3小时，慢慢减压至常压，并继续减压至0.05MPa脱水1小时后；放料切粒得到粒状的尼龙型共聚酰胺(PA-1)。按照国家标准GB/T3682-2000，测得PA-1的DSC终熔点为88℃，熔体流动速率为48g/10min/160℃/2.16kg。
制备新型热熔胶，将尼龙型共聚酰胺(PA-1)400g、过氯乙烯树脂117.46g、松香107.94g、乙烯基三甲氧基硅烷6.35g、己二酸二辛酯3.17g，投入到高速混合机中混合均匀；将混合后的物料投入到TE35双螺杆挤出机中，控制挤出机一区温度100℃，二区110℃，三至五区温度120℃，六区温度115℃，模头温度100℃，螺杆转速30r/min；出料后经流延冷却制成0.10mm的热熔胶膜。该胶膜样品标记为A1。
实施例2
制备尼龙型共聚酰胺：将己内酰胺106.4g、尼龙66盐170.5g、尼龙612盐107.35g和尼龙1010盐89.83g混合后，加入到一个带有搅拌器、温度表和压力表的2L高压反应釜中；再加入硬脂酸4.552g和去离子水80g，用氮气置换并抽真空，除尽反应釜中的空气；然后充入0.2MPa的高纯氮气，加热慢慢升温至230℃，在1.0-1.2MPa的压力下，保温反应3小时，慢慢减压至常压，并继续减压至0.05MPa脱水1小时后；放料切粒得到粒状的尼龙型共聚酰胺(PA-2)。按照国家标准GB/T3682-2000，测得PA-2的DSC终熔点为91℃，熔体流动速率为43.8g/10min/160℃/2.16kg。
制备新型热熔胶：将尼龙型共聚酰胺(PA-2)400g、过氯乙烯树脂88.24g、萜烯树脂94.12g、乙烯基三乙氧基硅烷2.94g、己二酸二辛酯2.94g，投入高速混合机混合均匀；将混合好的物料投入到TE35双螺杆挤出机中，共混熔融；出料后经流延冷却制成0.10mm的热熔胶膜。该胶膜样品标记为A2。
实施例3
制备尼龙型共聚酰胺：将己内酰胺87.78g、尼龙66盐173.12g、尼龙612盐138.52g和尼龙1010盐104.8g混合后，加入到一个带有搅拌器、温度表和压力表的2L高压反应釜中；再加入硬脂酸5.633g和去离子水60g，用氮气置换并抽真空，除尽反应釜中的空气；然后充入0.2MPa的高纯氮气，加热慢慢升温至230℃，在1.0-1.2MPa的压力下，保温反应3小时，慢慢减压至常压，并继续减压至0.05MPa脱水1小时后；放料切粒得到粒状的尼龙型共聚酰胺(PA-3)。按照国家标准GB/T3682-2000，测得PA-3的DSC终熔点为85℃，熔体流动速率为43.8g/10min/160℃/2.16kg。
制备新型热熔胶：将尼龙型共聚酰胺(PA-3)400g、过氯乙烯树脂89.71g、萜烯树脂74.29g、γ-氨基丙基三甲氧基硅烷1.71g、癸二酸二辛酯5.71g，投入高速混合机混合均匀；然后将混合好的物料投入到TE35双螺杆挤出机中， 共混熔融；出料后经流延冷却制成0.10mm的热熔胶膜。该胶膜样品标记为A3。
实施例4
制备尼龙型共聚酰胺：将己内酰胺97.09g、尼龙66盐167.87g、尼龙612盐107.35g和尼龙1010盐119.78g混合后，加入到一个带有搅拌器、温度表和压力表的2L高压反应釜中；再加入硬脂酸4.776g和去离子水70g，用氮气置换并抽真空，除尽反应釜中的空气；然后充入0.2MPa的高纯氮气，加热慢慢升温至230℃，在1.0-1.2MPa的压力下，保温反应3小时，慢慢减压至常压，并继续减压至0.05MPa脱水1小时后；放料切粒得到粒状的尼龙型共聚酰胺(PA-4)。按照国家标准GB/T3682-2000，测得PA-4的DSC终熔点为83℃，熔体流动速率为53.2g/10min/160℃/2.16kg。
制备新型热熔胶：将尼龙型共聚酰胺(PA-4)400g、过氯乙烯树脂125g、氢化石油树脂90g、N-(β-氨基乙基)-γ-氨基丙基三乙氧基硅烷6.25g、癸二酸二辛酯3.75g，投入高速混合机混合均匀；然后将混合好的物料投入到TE35双螺杆挤出机中，共混熔融；出料后经流延冷却制成0.10mm的热熔胶膜。该胶膜样品标记为A4。。
性能测试
所得各胶膜样品在80℃，0.3MPa，热压20s粘接PVC/铝和PVC/不锈钢的180°的剥离强度，测试方法参照GB/T2790-1995，测试结果见表1。
表1各实施例所得热熔胶膜对PVC/金属的粘结强度。
Figure PCTCN2016110282-appb-000001
Figure PCTCN2016110282-appb-000002
从上表中可看出，通过本发明所制备的新型热熔胶，对金属与PVC的粘接复合强度性能较好。且实际应用时，压烫温度较低，为80℃，不会对PVC材料造成损害；压烫时间亦较短，为20s，便于施工操作。

Claims (9)

  1. 一种新型热熔胶，其特征在于，其原料构成，按质量百分比计，包括：
    尼龙型共聚酰胺 63％～70％；
    过氯乙烯树脂 15％～20％；
    增粘剂 13％～17％；
    硅烷偶联剂 0.3％～1％；
    增塑剂 0.5％～1％；
    其中，所述尼龙型共聚酰胺由己内酰胺、尼龙66盐、尼龙612盐及尼龙1010盐四种主要原料在适量的水和硬脂酸作用下共聚而成，且所述四种主要原料的摩尔百分比分别为33％～40％、32％～38％、15％～20％及12％～16％；所述硬脂酸与所述己内酰胺的摩尔比为0.02:1～0.03:1。
  2. 如权利要求1所述的新型热熔胶，其特征在于：所述过氯乙烯树脂的氯含量为61％～65％。
  3. 如权利要求1所述的新型热熔胶，其特征在于：所述增粘剂选自松香、萜烯树脂或氢化石油树脂中的一种。
  4. 如权利要求1所述的新型热熔胶，其特征在于：所述硅烷偶联剂选自乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、N-(β-氨基乙基)-γ-氨基丙基三乙氧基硅烷或γ-氨基丙基三甲氧基硅烷中的一种。
  5. 如权利要求1所述的新型热熔胶，其特征在于：所述述增塑剂为己二酸二辛酯和癸二酸二辛酯中的一种。
  6. 如权利要求1～5任一项所述的新型热熔胶的制备方法，其特征在于，包括如下步骤：
    (1)按权利要求1～5任一项所述的新型热熔胶的原料构成，选取原料；
    (2)制备尼龙型共聚酰胺；
    (3)将所制备的尼龙型共聚酰胺与过氯乙烯树脂、增粘剂、硅烷偶联剂及增塑剂按预设配比加入到混合机中，搅拌均匀；
    (4)混合后的物料加入到双螺杆挤出机中，在100-130℃的温度下熔融挤出，即得新型热熔胶。
  7. 如权利要求6所述的新型热熔胶的制备方法，其特征在于，所述步骤(2)中，制备尼龙型共聚酰胺的方法依次包括如下步骤：
    (2a)将己内酰胺、尼龙66盐、尼龙612盐、尼龙1010盐按比例混合后，加入到高压反应釜中；
    (2b)向高压反应釜中加入硬脂酸及水，然后用氮气置换并抽真空，除尽反应釜中的空气；
    (2c)充入高纯氮气，加热升温至230℃，在1.0～1.2MPa压力下，保温反应3h，然后减压至常压，并继续减压至0.05MPa脱水1h；
    (2d)放料，即得所述尼龙型共聚酰胺。
  8. 如权利要求6所述的新型热熔胶的制备方法，其特征在于，还包括如下步骤：
    (5)所述新型热熔胶通过流延机流延或热熔涂布设备进行涂布，制成新型热熔胶膜。
  9. 一种新型热熔胶膜，其特征在于：通过权利要求8所述的新型热熔胶的制备方法制得，且所述新型热熔胶膜的厚度为0.1mm。
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CN105349088A (zh) * 2015-12-21 2016-02-24 上海天洋热熔粘接材料股份有限公司 一种新型热熔胶及其制备方法

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KR20180099746A (ko) 2018-09-05
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