WO2021051980A1 - 一种用于粘接三元乙丙橡胶的热熔胶膜 - Google Patents

一种用于粘接三元乙丙橡胶的热熔胶膜 Download PDF

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WO2021051980A1
WO2021051980A1 PCT/CN2020/102277 CN2020102277W WO2021051980A1 WO 2021051980 A1 WO2021051980 A1 WO 2021051980A1 CN 2020102277 W CN2020102277 W CN 2020102277W WO 2021051980 A1 WO2021051980 A1 WO 2021051980A1
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melt adhesive
adhesive film
hot melt
resin
epdm rubber
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PCT/CN2020/102277
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English (en)
French (fr)
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王学刚
蔡秀娟
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常州驰科光电科技有限公司
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10Homopolymers or copolymers of propene
    • C09J123/14Copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35Heat-activated
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304Additional 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00Presence of polyolefin
    • C09J2423/10Presence of homo or copolymers of propene

Definitions

  • the invention relates to the field of hot-melt adhesive film bonding, in particular to a hot-melt adhesive film for bonding EPDM.
  • EPDM is made by polymerizing ethylene and propylene monomers with a small amount of non-conjugated diene.
  • the characteristic of its structure is that there are no unsaturated double bonds in the main chain of the polymer molecule, but the introduction of unsaturated double bonds in the branch chain. Therefore, it has excellent weather resistance, heat resistance, ozone resistance, ultraviolet resistance, good processing performance and low compression set. It is the material of choice for the production of sealing strips. At present, most of the automotive sealing strip materials use EPDM as the main raw material. EPDM rubber strips are formed by microwave vulcanization process at one time.
  • the surface is smooth and beautiful, has good elasticity and resistance to compression deformation, weather resistance, ozone resistance, chemical resistance and a wide temperature range (-50°C) ⁇ +150°C) and other excellent performance, has been widely used in manufacturing industries such as automobile doors, windows, curtain walls
  • EPDM EPDM Due to the lack of active groups in the molecular structure of EPDM rubber, low cohesive energy, and the rubber is easy to bloom, self-adhesive and mutual adhesion are very poor, ordinary hot melt adhesive film is difficult to meet EPDM (EPDM)
  • EPDM EPDM
  • Patent CN201310674780.3 proposes a hot melt adhesive film for bonding EPDM rubber.
  • the hot melt adhesive film of this invention is tested under normal conditions.
  • the maximum peel force at 180 degrees is 85N
  • the maximum peel force is 59N after being stored at -40°C for 24 hours in low temperature
  • the maximum peel force is 60N after 96 hours of air circulation test at 100°C.
  • the patented EPDM rubber film (EPDM) is used for bonding automotive window flannel decorative sealing strips, and the bonding effect for door sealing strips, decorative strips, moldings and other sealing strips is average.
  • the purpose of the present invention is to provide a kind of easy bonding, high bonding strength, no solvent cleaning, no primer treatment, direct composite bonding at high temperature after vulcanization of EPDM rubber, which can meet the requirements of automotive EPDM Hot-melt adhesive film required for the bonding strength of rubber sealing strips.
  • the hot-melt adhesive film of the invention has the advantages of higher bonding strength of EPDM, simple use process, more environmental protection and more convenient, and can meet the requirements of automotive sealing and bonding of EPDM sealing strips.
  • the present invention is realized through the following process:
  • a hot-melt adhesive film for bonding EPDM rubber is composed of 30-65 parts of polyolefin resin, 15-45 parts of tackifying resin, 3-12 parts of functional filler, 3 -10 parts of curing agent and 1-5 parts of adhesion promoter, after mixing, screw extrusion molding.
  • the polyolefin resin is one or a mixture of amorphous propylene copolymer APAO, polyolefin, styrene TPE, or polyurethane TPE.
  • the tackifying resin is natural rosin resin, C5 petroleum resin, C9 petroleum resin, C5/C9 petroleum resin, ⁇ -terpene resin, ⁇ -terpene resin, terpene phenol resin or terpene phenol modified petroleum resin At least one of.
  • the functional filler is at least one of calcium carbonate, silica powder, talc, white carbon black, or light white carbon black.
  • the functional curing agent is at least one of isocyanate, melamine resin or melamine resin.
  • the adhesion promoter is a silane coupling agent.
  • the polyolefin resin, tackifying resin, functional filler and adhesion promoter are mixed uniformly in the mixer without granulation treatment.
  • the mixture is directly placed in the screw extruder and extruded at 170-200°C. Melt film.
  • the thickness of the hot melt adhesive film is 30-200 ⁇ m.
  • one side of the film When in use, one side of the film is compounded with 1.0-2.0mm thick acrylic foam, and the other side is directly compound bonded at high temperature after vulcanization of EPDM.
  • the hot-melt adhesive film of the present invention is used for bonding EPDM rubber with strong bonding force and can meet the requirements of the adhesive peeling force of the automobile industry standard without strengthening treatment; it is convenient to use, and EPDM rubber (EPDM ) No solvent cleaning, no primer treatment, direct compound bonding at high temperature after vulcanization of EPDM rubber, which greatly improves the production efficiency of large-scale mass production.
  • amorphous propylene copolymer (APAO), 15 parts of petroleum resin C9, 10 parts of terpene phenolic resin, 8 parts of light white carbon black, 5 parts of isocyanate, and 2 parts of silane coupling agent in the mixer , Stir and mix for 30 minutes.
  • APAO amorphous propylene copolymer
  • 15 parts of petroleum resin C9, 10 parts of terpene phenolic resin, 8 parts of light white carbon black, 5 parts of isocyanate, and 2 parts of silane coupling agent in the mixer Stir and mix for 30 minutes.
  • the mixed homogeneous material in the screw extruder and extrude 50um hot melt adhesive film at 180°C.
  • One side of the film is glued to the surface of 1.0mm acrylic foam, and the other side is directly bonded to the EPDM rubber at high temperature after vulcanization.
  • the 180 degree peel force is 100N in the normal test, and the peel force is tested after low temperature storage at -40°C for 24 hours.
  • amorphous propylene copolymer (APAO), 15 parts of petroleum resin C9, 15 parts of ⁇ -terpene resin, 8 parts of light white carbon black, 5 parts of isocyanate, and 2 parts of silane coupling agent in the mixer Inside, stir and mix for 30 minutes. After the raw materials are uniformly mixed, place the mixed homogeneous material in a screw extruder, and extrude a 50um hot melt adhesive film at 180°C. One side of the adhesive film is glued to the surface of 1.0mm acrylic foam, and the other side is directly composite bonded with EPDM rubber at high temperature after vulcanization. Normal test 180 degree peel force is 98N, -40 °C 24 hours low temperature storage test peel force After the air circulation test at a high temperature of 100°C for 96 hours, the peeling force was 66N.
  • APAO amorphous propylene copolymer

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

Abstract

一种用于粘接三元乙丙橡胶(EPDM)的热熔胶膜,该热熔胶胶膜由30-65份聚烯烃类树脂,15-45份增粘树脂,3-12份功能性填料,3-10份固化剂,1-5份助粘剂,经混炼,螺杆挤出制模成型。所述热熔胶膜用于粘接三元乙丙橡胶,粘接力强,无需加强处理,即可满足汽车行业标准的粘接剥离力要求;使用方便,使用时三元乙丙橡胶(EPDM)不用溶剂清洗,不用底涂剂处理,在三元乙丙橡胶硫化后高温时直接复合粘接,很好的提高了大规模量产的生产效率。

Description

一种用于粘接三元乙丙橡胶的热熔胶膜 技术领域
本发明涉及热熔胶膜粘接领域,尤其涉及一种用于粘接三元乙丙橡胶(EPDM)的热熔胶膜。
背景技术
三元乙丙橡胶(EPDM)系由乙烯、丙烯单体加入少量非共轭二烯烃聚合而成。其结构的特点是在聚合物分子主链上无不饱和双键,而在支链上引入了不饱和双键。因而具有优良的耐天候性、耐热性、耐臭氧、耐紫外线性以及良好的加工性能和低压缩永久变形,是生产密封条的首选材料。目前,汽车密封条材料绝大部分都是采用EPDM作为主要原料。三元乙丙(EPDM)胶条采用微波硫化工艺一次成型,表面光洁美观,具有良好的弹性和抗压缩变形,耐天候老化、耐臭氧、耐化学作用及较宽的使用温度范围(-50℃~+150℃)等优异性能,已被汽车门窗幕墙等制造业广泛应用。
由于三元乙丙橡胶分子结构缺少活性基团,内聚能低,加上胶料易于喷霜,自粘性和互粘性很差,普通的热熔胶膜很难满足三元乙丙(EPDM)胶条粘接的要求,强度无法达到汽车行业的要求(常态测试180度剥离力大于45N,-40℃24小时低温存放后测试剥离力大于30N以及100℃高温96小时空气循环试验后大于30N,测试方法参照GB/T2790)。
目前汽车密封条通常采用三元乙丙橡胶表面用溶剂清洗以及打磨后用底涂剂打上底涂,然后再用普通热熔胶膜粘接的工艺进行粘接。此工艺使用溶剂胶水,对工人身体不利,对环境不利;而且工艺流线长,工艺复杂,成品率低。
近年来,对于三元乙丙橡胶热熔粘接的研究并不多,专利CN201310674780.3提出了一种用于粘接三元乙丙橡胶的热熔胶膜,该发明热熔胶膜常态测试180度剥离力最大为85N,-40℃24小时低温存放后测试剥离力最大为59N,100℃高温96小时空气循环试验后,剥离力最大为60N。该专利发明三元乙丙橡胶的热熔胶膜(EPDM)为粘接汽车车窗绒布装饰密封条所用,对于车门密封条、装饰条、嵌条和其他密封条的粘接效果一般。
发明内容
本发明目的在于提供一种易于粘接,且粘接强度大,不用溶剂清洗,不用底涂剂处理,在三元乙丙橡胶硫化后高温时直接复合粘接,可以满足车用三元乙丙橡胶密封条的粘接强度要求的热熔胶膜。该发明热熔胶膜优点在于粘接三元乙丙橡胶(EPDM)强度更高,使用工艺简单,更环保,更方便,可以实现三元乙丙橡胶密封条的车用密封粘接要求。
本发明是通过以下过程实现的:
一种用于粘接三元乙丙橡胶的热熔胶膜,该热熔胶胶膜由30-65份聚烯烃类树脂,15-45份增粘树脂,3-12份功能性填料,3-10份固化剂和1-5份的助粘剂,经混炼,螺杆挤出制模成型。
所述的聚烯烃类树脂为非晶态丙烯共聚物APAO、聚烯烃、苯乙烯类TPE、或聚氨酯类TPE中的一种或几种混合。
所述的增粘树脂为天然松香类树脂、C5石油树脂、C9石油树脂、C5/C9石油树脂、α-萜烯树脂、β-萜烯树脂、萜烯酚醛树脂或萜烯酚改性石油树脂的至少一种。
所述的功能性填料为碳酸钙、硅微粉、滑石粉、白碳黑、或轻质白碳黑的至少一种。
所述的功能性固化剂为异氰酸酯、三聚氰胺树脂或密胺树脂的至少一种。
所述的助粘剂为硅烷偶联剂。
将聚烯烃类树脂,增粘树脂,功能填料和助粘剂在混料机内混炼均匀,无需造粒处理,直接将混合料置于螺杆挤出机中,在170-200℃挤出热熔胶膜。
热熔胶膜的厚度为30-200μm。
使用时,胶膜一面复合1.0-2.0mm厚度的亚克力泡棉,另一面在三元乙丙橡胶硫化后高温时直接复合粘接。
本发明热熔胶膜用于粘接三元乙丙橡胶,粘接力强,无需加强处理,即可满足汽车行业标准的粘接剥离力要求;使用方便,使用时三元乙丙橡胶(EPDM)不用溶剂清洗,不用底涂剂处理,在三元乙丙橡胶硫化后高温时直接复合粘接,很好的提高了大规模量产的生产效率。
具体实施方式
具体实施例1
将45份非晶态丙烯共聚物(APAO),15份石油树脂C9,10份萜烯酚醛树脂,8份的轻质白炭黑,5份异氰酸酯,2份硅烷偶联剂在混料机内,搅拌混合30分钟,待原料混和均匀,将混合均匀料置于螺杆挤出机中,在180℃挤出50um热熔胶膜。将胶膜一面粘于1.0mm亚克力泡棉表面,另一面与三元乙丙橡胶硫化后高温时直接复合粘接,常态测试180度剥离力为100N,-40℃24小时低温存放后测试剥离力为65N,100℃高温96小时空气循环试验后,剥离力为68N。
具体实施例2
将45份非晶态丙烯共聚物(APAO),15份石油树脂C9,15份α-萜烯树脂,8份的轻质白炭黑,5份异氰酸酯,2份硅烷偶联剂在混料机内,搅拌混合30分钟,待原料混和均匀,将混合均匀料置于螺杆挤出机中,在180℃挤出50um热熔胶膜。将胶膜一面粘于1.0mm亚克力泡棉表面,另一面与三元乙丙橡胶硫化后高温时直接复合粘接,常态测试180度剥离力为98N,-40℃24小时低温存放后测试剥离力为69N,100℃高温96小时空气循环试验后,剥离力为66N。

Claims (9)

  1. 一种用于粘接三元乙丙橡胶的热熔胶膜,其特征在于,该热熔胶胶膜由30-65份聚烯烃类树脂,15-45份增粘树脂,3-12份功能性填料,3-10份固化剂和1-5份助粘剂,经混炼,螺杆挤出制模成型。
  2. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:所述的聚烯烃类树脂为非晶态丙烯共聚物APAO、聚烯烃、苯乙烯类TPE、或聚氨酯类TPE中的一种或几种混合。
  3. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:所述的增粘树脂为天然松香类树脂、C5石油树脂、C9石油树脂、C5/C9石油树脂、α-萜烯树脂、β-萜烯树脂、萜烯酚醛树脂或萜烯酚改性石油树脂的至少一种。
  4. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:所述的功能性填料为碳酸钙、硅微粉、滑石粉、白碳黑、或轻质白碳黑的至少一种。
  5. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:所述的功能性固化剂为异氰酸酯、三聚氰胺树脂或密胺树脂的至少一种。
  6. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:所述的助粘剂为硅烷偶联剂。
  7. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:将聚烯烃类树脂,增粘树脂,功能填料和助粘剂在混料机内混炼均匀,无需造粒处理,直接将混合料置于螺杆挤出机中,在170-200℃挤出热熔胶膜。
  8. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:热熔胶膜的厚度为30-200μm。
  9. 根据权利要求1所述的粘接三元乙丙橡胶的热熔胶膜,其特征在于:使用时,胶膜一面复合1.0-2.0mm厚度的亚克力泡棉,另一面在三元乙丙橡胶硫化后高温时直接复合粘接。
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CN115710475A (zh) * 2022-12-26 2023-02-24 牛牧 一种耐高温三元乙丙橡胶与丙烯酸胶带的助粘剂

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