CN114040955A - 单组分可热活化聚氨酯水基粘合剂组合物 - Google Patents
单组分可热活化聚氨酯水基粘合剂组合物 Download PDFInfo
- Publication number
- CN114040955A CN114040955A CN202080047673.6A CN202080047673A CN114040955A CN 114040955 A CN114040955 A CN 114040955A CN 202080047673 A CN202080047673 A CN 202080047673A CN 114040955 A CN114040955 A CN 114040955A
- Authority
- CN
- China
- Prior art keywords
- adhesive composition
- polyurethane
- weight
- composition according
- dry matter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/778—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur silicon
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—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
- C09J11/02—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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives 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
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
-
- 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
- C08G2170/00—Compositions for adhesives
- C08G2170/80—Compositions for aqueous adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C09J2423/00—Presence of polyolefin
-
- 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
- C09J2427/006—Presence of halogenated polymer in the substrate
-
- 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
- C09J2431/00—Presence of polyvinyl acetate
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
单组分可热活化聚氨酯水基粘合剂组合物,其相对于粘合剂组合物的总重量包含:‑按干物质重量计,12%至50%的包含烷氧基硅烷基侧链和/或末端基团的聚氨酯(A)的水分散体,和‑0.5重量%至5重量%的缩水甘油氧基官能度至少为2的缩水甘油氧基取代的烷氧基硅烷化合物(B)。
Description
本发明涉及单组分可热活化聚氨酯水基粘合剂组合物,其适合用作热成型层压粘合剂。
热成型或真空成型基本上是取一片热塑性片材(或箔),将其加热到超过其软化点的点,将其抽真空至由一些热塑性材料制成的基材的三维轮廓表面,和冷却成型的片材回至低于其软化点。
可以对多种热塑性材料进行这种处理。热成型中使用的一些常用材料列举如下:
-高抗冲聚苯乙烯(HIPS)
-丙烯腈-丁二烯-苯乙烯(ABS)
-苯乙烯-丙烯腈(SAN)
-聚氯乙烯(PVC)
-聚碳酸酯(PC)
-高密度聚乙烯(HDPE)
-聚苯醚(PPO)。
这种成型技术特别用于通过使用称为热成型层压粘合剂的特殊类别的粘合剂将装饰性可膨胀热塑性覆盖材料(例如PVC箔)层压到三维轮廓的热塑性或纤维板基材上。
通常,首先通过喷涂将热成型层压粘合剂施加到基材的三维轮廓表面,然后加热以在所述表面上形成干燥的粘合剂层。然后,考虑到其热活化,将该干燥的粘合剂层加热,并且在热成型操作期间,将热塑性箔在压力下结合到所述表面上,导致形成连接所述表面和箔的高强度结合。
这种方法已广泛用于生产用于汽车工业的内饰设备。一些典型的应用包括在例如汽车车顶、门板、仪表板和中央控制台、仪表盘、遮阳板或方向盘的制造中PVC膜的热成型层压。
已知可热活化(有时,相当不合适地,也称为“热活化的”)聚氨酯溶剂基粘合剂组合物用作热成型层压粘合剂。
由于生态原因,多年来一直存在用可热活化的聚氨酯水基粘合剂分散体替代这种溶剂基粘合剂组合物的趋势,该可热活化的聚氨酯水基粘合剂分散体在实施时也需要干燥步骤,然后是干燥的粘合剂膜的热活化步骤。
目前,许多汽车供应商主要使用双组分(也称为“2K”)水性粘合剂制造例如以上所述的汽车内饰设备,该双组份水性粘合剂包含可热活化的水基聚氨酯分散体和水分散的异氰酸酯固化剂,后者也称为“硬化剂”。
在施加在待结合的基材上之前,这两种组分在汽车供应商处现场混合。
通过将热塑性箔连接到涂有粘合剂的基材的三维轮廓表面上形成的结合由聚氨酯和硬化剂之间的固化(或交联)反应产生。这种交联反应需要一些时间来发展,直到获得完全固化的粘合剂连接。
必须在几天的短时间后获得对应于完全固化的粘合剂连接的高最终强度,以便相应的汽车装饰设备可以尽可能快得发送给汽车制造商,从而减少了将所述制品存放在汽车供应商场地的工业场地以完成固化的需要。特别地,在室温下储存汽车设备一天之后获得非常高的最终强度是非常期望的。
除了最终强度之外,将热塑性箔与基材的三维轮廓表面连接在一起的结合的初始强度也是非常重要的要求。
该初始强度(有时也用术语“生强度”表示)是在第一次接触时并且在粘合剂发展出其当完全固化时的最终结合性质之前粘合剂将两个表面保持在一起的能力。
实际上,高生强度粘合剂在层压过程期间倾向于防止乙烯基箔的起皱和滑动。它们还确保所述膜快速且牢固地固定在基材的三维轮廓以及有时几何复杂表面上。这进而允许在自动化制造过程期间将得到的组装体在组装线上作为单个设备来处理,从而确保其高生产率。
然而,2K水性粘合剂的混合步骤需要额外的过程和设备,这意味着更高的成本。
此外,一旦混合了两种组分,所得到的单一组合物可能遇到稳定性问题,直到它可以有效地实施(取决于生产限制)。这些问题可严重地限制所述组合物的适用期(所述组合物必须保存在储罐中)到几小时,通常不超过8小时,并且在夏季高温期间甚至更少。必须丢弃在适用期期间未使用的该单一组合物。
随着通过喷涂进行的自动粘合剂施加系统变得越来越多地在汽车供应商工业场地实施,还存在这样的问题:由两种组分的混合产生的不稳定的单一组合物可能阻塞粘合剂供应系统和管道,尤其是在夏季。
最后,由于硬化剂是异氰酸酯基的,因此还存在其可能对工业场地的工人造成过敏问题的问题。
已知一些单组分(也称为“1K”)可热活化聚氨酯水基粘合剂组合物,其避免了2K组合物的缺点。
中国专利申请CN 106675492提到了这种1K水基组合物,其包含聚氨酯分散体、乙烯乙酸乙烯酯(或EVA)分散体和水基封端多异氰酸酯交联剂作为必要成分。然而,该文献没有指出相应结合基材的粘合强度的任何结果。
本发明的一个目的是提供一种单组分可热活化聚氨酯水基粘合剂组合物,其允许以改进的粘合强度连接两个基材。
本发明的另一个目的是提供一种单组分可热活化聚氨酯水基粘合剂组合物,当其用作热成型层压粘合剂时,提供高生强度(或初始强度)以及改善的最终强度。
现已发现,上述目的可以全部或部分地通过作为本发明的主题的单组分可热活化聚氨酯水基粘合剂组合物实现。
根据第一个目的,本发明涉及单组分可热活化聚氨酯水基粘合剂组合物,其相对于粘合剂组合物的总重量包含:
-按干物质的重量计,12%至50%的包含烷氧基硅烷基侧链和/或末端基团的聚氨酯(A)的水分散体,和
-0.5重量%至5重量%的缩水甘油氧基官能度为至少2的缩水甘油氧基取代的烷氧基硅烷化合物(B)。
这种聚氨酯(A)还特别包括聚(氨酯-脲)。
所述聚氨酯(A)的水基分散体是已知的,特别是来自WANHUA的PCT申请WO 2018/120055,并且可以如所述申请中所述进行制备,该申请在此引入作为参考。
根据一个优选的实施方案,聚氨酯(A)的水基分散体是含水阴离子脂族聚氨酯水分散体。
根据另一个优选的实施方案,包含在聚氨酯(A)的烷氧基硅烷基侧链和/或末端基团中的烷氧基基团选自甲氧基或乙氧基基团。
这些分散体有时被称为可自交联的聚氨酯分散体,因为它们可一旦施加在基材上,就被干燥然后通过加热活化以进行交联反应并固化,而不需要硬化剂。
不受任何理论机理的束缚,据信在作为热成型层压粘合剂实施的干燥和热活化步骤中,聚合物(A)的烷氧基硅烷基侧链和/或末端基团经历快速水解,导致相应的聚氨酯主链的交联。
出人意料地,发现在根据本发明的组合物中,所述聚合物(A)与所述特定硅烷化合物(B)的组合导致结合的基材的改进的最终强度,同时还提供适当的初始强度。实际上,当作为热成型层压粘合剂实施时,根据本发明的组合物使得可以实现有利地大于15N/25 mm的初始强度(通过在ABS基材上层压PVC箔后1分钟进行的剥离试验测量)。其还使得可以实现有利地大于50N/25mm,并且甚至更优选大于85N/25mm的最终强度(通过在层压后在室温下储存相同层压材料1天后进行的剥离试验测量)。
此外,根据本发明的1K组合物不存在2K组合物的适用期问题,并且有利地具有至少6个月的保质期。
具体的硅烷化合物(B)是具有至少2的缩水甘油氧基官能度的缩水甘油氧基取代的硅烷化合物(B)。
缩水甘油氧基具有下式:
并且由这些基团取代的硅烷是本领域技术人员所熟知的。它们可在市场上购买到。
根据一个优选的实施方案,硅烷化合物(B)具有至少3,并且甚至更优选至少4的缩水甘油氧基官能度。
根据另一个优选的实施方案,相对于所述粘合剂组合物的总重量,根据本发明的水基粘合剂组合物还包含以干物质重量计8-30%的乙酸乙烯酯和乙烯(VAE)共聚物(C)的水乳液。VAE水乳液基于乙酸乙烯酯和乙烯的共聚合,其中乙酸乙烯酯含量可以为60-95重量%,并且乙烯含量为5-40重量%,基于单体的总重量计算。
根据一个更优选的实施方案,将在根据本发明的组合物中作为水乳液包含的VAE(C)共聚物是这样的:
-(C)的55%重量/重量干物质水分散体的布鲁克菲尔德粘度在25℃下大于1000mPa.s;和/或
-其玻璃化转变温度(Tg)低于10℃。
以本领域技术人员公知的标准方式,玻璃化转变温度可通过DSC(差示扫描量热法)测量。
根据一个甚至更优选的实施方案,将在根据本发明的组合物中作为水乳液包含的VAE(C)是这样的:
-(C)的55%重量/重量干物质水分散体的布鲁克菲尔德粘度在25℃下大于4000mPa.s,优选4500-12000mPa.s;和/或
-其玻璃化转变温度(Tg)大于0℃,优选0℃-10℃。
然后特别改善了连接两个基材的结合的最终强度。
VAE乳液在市场上广泛可得。作为例子可以提及以下这些:
-来自DAIREN CHEMICAL的DA 104,其为55%重量/重量的VAE水分散体,根据ISO2555:2018在25℃下的粘度为2000-3000mPa.s并且Tg在-20℃至-10℃之间。
根据另一个实施方案,根据本发明的水基粘合剂组合物可包含按干物质计最高达15重量%的非硅烷基化的聚氨酯(D)的水分散体,优选非硅烷基化的阴离子聚氨酯分散体,所述百分比相对于粘合剂组合物的总重量表示。
适合作为热成型层压粘合剂的非硅烷基化聚氨酯的水分散体是本领域公知的,并且例如在BAYER的专利申请US 2005/0131109中有描述。市场上有许多商业产品。作为例子,可以提及COVESTRO的U XP 2682,其是基于聚酯多元醇和脂族多异氰酸酯的50%重量/重量的阴离子聚氨酯水分散体。
根据一个甚至更优选的实施方案,根据本发明的水基粘合剂组合物可包含以干物质计3至13重量%的(D)的水分散体,对应于甚至更加改善的最终强度值。
根据本发明的组合物可任选地包含少量选自以下中的一种或多种的成分:pH调节剂,杀生物剂,染料或颜料,增稠剂,润湿剂,消泡剂。对于少量,这些成分的含量意指在0.01重量%至0.5重量%之间,所述百分比相对于粘合剂组合物的总重量表示。
在一些应用中,一旦施加在基材的三维轮廓表面上,可视化所述粘合剂可能是特别有利的,尤其是对于确定热成型粘合剂是否已被均匀施加。对于这些应用,可以将颜料或染料掺入根据本发明的水基组合物中。对于这种用途很多种相容颜料是市售可得的。作为一个例子,可以提及水分散的酞菁蓝颜料,例如来自CHROMAFLO的Blue C6。
可以将增稠剂添加到根据本发明的粘合剂组合物,以便例如当要将所述粘合剂施加到要与装饰性可膨胀乙烯基覆盖箔层压的基材的倾斜或垂直表面上时将其粘度增加至所需水平,以降低其流失趋势。有用的增稠剂可包括丙烯酸酯增稠剂或聚氨酯基增稠剂,例如ELEMENTICS的WT-180F。
最后,有用的消泡剂包括有机改性的硅氧烷,例如来自RHODIA的ANTIFOAM 691。
在根据本发明的粘合剂组合物中,水通过以下提供:聚氨酯(A)的水乳液、VAE共聚物(C)的水乳液、非硅烷基化聚氨酯(D)的水分散体、任选成分中存在的水和任选添加的水。实际上,取决于各种成分的稀释度,可以加入水以获得所需浓度的活性物质。
根据一个实施方案,水占粘合剂组合物总重量的20重量%至60重量%,优选占粘合剂组合物总重量的30重量%至50重量%。
根据一个特别优选的实施方案,根据本发明的粘合剂组合物包含:
-以干物质重量计12%至40%的聚氨酯(A)的水分散体;
-0.5重量%至2重量%的缩水甘油氧基官能度至少为2的缩水甘油氧基取代的烷氧基硅烷化合物(B);
-以干物质重量计9%至28%的VAE共聚物(C)的水乳液;和
-以干物质重量计3-13%的非硅烷基化聚氨酯(D)的水分散体。
根据第二个目的,本发明涉及制备可热活化聚氨酯水基粘合剂组合物的方法,该组合物例如如以上所限定,所述方法包括以下步骤:
(i)当存在时,将VAE共聚物(C)的水乳液在搅拌下引入混合容器中;然后
(ii)在持续搅拌下将聚氨酯(A)的水分散体引入所述容器中,搅拌保持例如约30至60分钟;然后
(iii)仍然在搅拌下将硅烷化合物(B)引入所述容器中,搅拌保持例如约30分钟;
优选地,在步骤(i)中,在步骤(ii)之前,在引入共聚物(C)之后引入pH调节剂(当存在于粘合剂组合物中时),保持搅拌(例如在约300-500转/分钟的旋转速度下进行)在约30分钟的时间。
根据另一个优选的实施方案,在步骤(ii)和(iii)之间,将杀生物剂、润湿剂和/或消泡剂(当存在时)在持续搅拌下引入所述混合容器中,搅拌保持例如约30至60分钟。
根据一个进一步优选的实施方案,在步骤(iii)之后任选地在持续搅拌下将增稠剂和/或颜料(或染料)(当存在时)引入所述容器中,搅拌保持例如约30至60分钟。
上述方法的步骤优选在室温下进行,并且在所述方法后获得的组合物有利地进行80目筛网过滤。
根据第三个目的,本发明涉及一种通过热成型层压连接基材和装饰性可膨胀热塑性覆盖材料的方法,所述方法包括以下步骤:
(a)将可热活化的聚氨酯水基粘合剂组合物(例如如上所述)施加在所述基材的表面上;
(b)干燥施加的组合物以除去水;然后
(c)通过热成型层压工艺将可膨胀热塑性覆盖材料施加在涂有干燥的粘合剂组合物的基材表面上。
因为是水基的,所以根据本发明的组合物与各种基材相容,所述基材包括木材、刨花板、胶合板和大多数热塑性材料。优选地,基材是不可膨胀的刚性基材。
在可膨胀的热塑性覆盖材料中,PVC箔是优选的。
所述粘合剂组合物可以通过任何所需的方式施加在所述基材的表面上,例如刷涂、浸涂、辊涂、或优选通过喷涂。要施加的所述粘合剂组合物的量可以在50至200g/m2的范围内变化,以湿量表示,取决于应用和基材。
一旦如步骤(a)中那样施用,则然后将水基粘合剂组合物进行干燥步骤(b),其中可以在室温或升高的温度下除去水。基于粘合剂组合物的性质选择干燥温度;在较低温度下干燥需要较长时间。
在步骤(c)中通过使用标准热成型层压技术施加可膨胀热塑性覆盖材料,优选PVC箔,其包括在压力和加热下压制热塑性覆盖材料和基材。
以下实施例纯粹是为了说明本发明而给出,并且在任何情况下都不应解释为限制本发明范围。
实施例1-5(根据本发明)
表1中实施例1-5的水基粘合剂组合物是通过在搅拌下简单混合它们的成分制备的,如上文在根据本发明的方法的详细描述中所指出的。
这些粘合剂组合物中的每一种都通过热成型层压制备层压材料,如下所述。
作为基材,使用10cm边长和3mm厚的方形ABS板,并且作为热塑性覆盖物,使用22cm长、2.5cm宽和1.5mm厚的PVC箔。
将每种组合物以控制的涂层重量喷涂在ABS刚性基材上,涂层重量范围为100-120g/rn2(作为湿量表示)。然后,将涂覆的ABS基材置于50℃烘箱中10分钟,以进行干燥。然后将PVC箔热压到干燥的涂覆的ABS基材上,实验室压机的上板和下板都在70℃的温度,并且在2MPa的标称压力下保持10秒。
将如此制备的层压材料在Instron拉伸强度测试仪上进行180°剥离试验,夹具速度设定为300mm/min。在制备后使层压材料在室温下静置以下时间后进行该试验:1分钟(评估初始强度)或1天(评估最终强度)。
获得的结果以N/25mm表示并收集在表1中。
所有实施例都显示1分钟后180°剥离结果大于15N/25mm,这被认为是非常合适的。
此外,对于所有实施例,1天后的180°剥离结果大于50N/25mm,这对应于非常好的最终强度。
另外,对于实施例3、4和5,最终强度甚至更加得以改善,大于85N/25mm。对于这3个实施例,还观察到PVC表皮的基材失效(表1中记载的SF),这意味着在剥离操作期间,所述PVC表皮在其评估表面的一定百分比上被撕裂,同样在表1中在SF字母之前给出。对应的层压材料的这种失效模式与实施例1和2中观察到的粘合剂失效模式形成对比,并且指向层压材料的粘合结合的优异结构完整性程度。
实施例A-C(对比)
剥离测试结果也显示在表1中。
1天后的剥离值小于50N/25mm,这被认为是非常不合适的。
Claims (12)
1.单组分可热活化聚氨酯水基粘合剂组合物,其相对于粘合剂组合物的总重量包含:
-按干物质重量计,12%至50%的包含烷氧基硅烷基侧链和/或末端基团的聚氨酯(A)的水分散体,和
-0.5重量%至5重量%的缩水甘油氧基官能度至少为2的缩水甘油氧基取代的烷氧基硅烷化合物(B)。
2.根据权利要求1的单组分粘合剂组合物,其特征在于聚氨酯(A)的水基分散体是含水阴离子脂族聚氨酯水分散体。
3.根据权利要求1和2中任一项的单组分粘合剂组合物,其特征在于包含在聚氨酯(A)的烷氧基硅烷基侧链和/或末端基团中的烷氧基基团选自甲氧基或乙氧基基团。
4.根据权利要求1-3中任一项的单组分粘合剂组合物,其特征在于硅烷化合物(B)具有至少3的缩水甘油氧基官能度。
5.根据权利要求1至4中任一项的单组分粘合剂组合物,其特征在于,相对于所述粘合剂组合物的总重量,其还包含以干物质重量计8至30%的乙酸乙烯酯和乙烯(VAE)的共聚物(C)的水乳液。
6.根据权利要求5的单组分粘合剂组合物,其特征在于VAE(C)是这样的:
-55%重量/重量干物质的(C)水分散体的布鲁克菲尔德粘度在25℃大于4000mPa.s;和/或
-其玻璃化转变温度(Tg)大于0℃。
7.根据权利要求1至6中任一项的单组分粘合剂组合物,其特征在于包含按干物质重量计最高达15重量%的非硅烷基化的聚氨酯(D)的水分散体。
8.根据权利要求1-7中任一项的单组分粘合剂组合物,其特征在于水占粘合剂组合物总重量的20-60重量%。
9.根据权利要求5至8中任一项的单组分粘合剂组合物,其特征在于其包含:
-以干物质重量计12%至40%的聚氨酯(A)的水分散体;
-0.5重量%至2重量%的化合物(B);
-以干物质重量计9%至28%的VAE共聚物(C)的水乳液;和
-以干物质重量计3-13%的非硅烷基化聚氨酯(D)的水分散体。
10.制备可热活化聚氨酯水基粘合剂组合物的方法,例如如权利要求1至9中任一项所限定的粘合剂组合物,所述方法包括以下步骤:
(i)当存在时,将VAE共聚物(C)的水乳液在搅拌下引入混合容器中;然后
(ii)在持续搅拌下将聚氨酯(A)的水分散体引入所述容器中;然后
(iii)仍然在搅拌下将硅烷化合物(B)引入所述容器中。
11.通过热成型层压连接基材和装饰性可膨胀热塑性覆盖材料的方法,所述方法包括以下步骤:
(a)将可热活化聚氨酯水基粘合剂组合物,例如如权利要求1至9中任一项所限定的,施加在所述基材的表面上;
(b)干燥施加的组合物以除去水;然后
(c)通过热成型层压工艺将可膨胀热塑性覆盖材料施加在用干燥的粘合剂组合物涂覆的基材表面上。
12.根据权利要求11所述的方法,其特征在于,所述可膨胀热塑性覆盖材料是PVC箔。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19185812.5 | 2019-07-11 | ||
EP19185812.5A EP3763525A1 (en) | 2019-07-11 | 2019-07-11 | One-component heat-activatable polyurethane water-based adhesive composition |
PCT/EP2020/069038 WO2021005018A1 (en) | 2019-07-11 | 2020-07-06 | One-component heat-activatable polyurethane water-based adhesive composition |
Publications (1)
Publication Number | Publication Date |
---|---|
CN114040955A true CN114040955A (zh) | 2022-02-11 |
Family
ID=67253795
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202080047673.6A Pending CN114040955A (zh) | 2019-07-11 | 2020-07-06 | 单组分可热活化聚氨酯水基粘合剂组合物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US20220315816A1 (zh) |
EP (2) | EP3763525A1 (zh) |
CN (1) | CN114040955A (zh) |
WO (1) | WO2021005018A1 (zh) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1834128A (zh) * | 2005-03-16 | 2006-09-20 | 住友化学株式会社 | 水乳液及其生产方法 |
CN101490197A (zh) * | 2006-07-12 | 2009-07-22 | 巴斯夫欧洲公司 | 含硅烷化合物作为添加剂的聚氨酯粘合剂 |
US20130158159A1 (en) * | 2011-12-19 | 2013-06-20 | Momentive Performance Materials Inc. | Epoxy-containing polysiloxane oligomer compositions, process for making same and uses thereof |
CN105814254A (zh) * | 2013-11-18 | 2016-07-27 | 莫梅特公司 | 金属化织物及其制造方法 |
CN107109114A (zh) * | 2014-12-26 | 2017-08-29 | Posco公司 | 耐黑变性和耐蚀性优异的无铬涂覆组合物及表面处理钢板 |
CN108463544A (zh) * | 2015-12-11 | 2018-08-28 | 博斯蒂克股份公司 | 涂覆工业生产线的清洁组合物 |
WO2018178165A1 (en) * | 2017-03-29 | 2018-10-04 | Sika Technology Ag | Water-based composition having improved mechanical properties |
CN109868107A (zh) * | 2017-12-01 | 2019-06-11 | 万华化学(宁波)有限公司 | 一种粘合剂及其制备方法和应用 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10343675A1 (de) | 2003-09-18 | 2005-04-14 | Bayer Materialscience Ag | Wässrige Klebstoff-Dispersionen |
DE10352177A1 (de) * | 2003-11-05 | 2005-06-02 | Röhm GmbH & Co. KG | Antistatisch beschichteter Formkörper und Verfahren zu seiner Herstellung |
CN108250390B (zh) | 2016-12-29 | 2020-07-28 | 万华化学集团股份有限公司 | 一种聚氨酯或聚氨酯-脲的水分散体、制备方法和用途 |
CN106675492A (zh) | 2017-01-06 | 2017-05-17 | 上海汉司实业有限公司 | 一种单组份水性聚氨酯汽车内饰粘合剂及其制备方法 |
-
2019
- 2019-07-11 EP EP19185812.5A patent/EP3763525A1/en not_active Withdrawn
-
2020
- 2020-07-06 US US17/617,974 patent/US20220315816A1/en active Pending
- 2020-07-06 WO PCT/EP2020/069038 patent/WO2021005018A1/en unknown
- 2020-07-06 EP EP20737013.1A patent/EP3996919A1/en active Pending
- 2020-07-06 CN CN202080047673.6A patent/CN114040955A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1834128A (zh) * | 2005-03-16 | 2006-09-20 | 住友化学株式会社 | 水乳液及其生产方法 |
CN101490197A (zh) * | 2006-07-12 | 2009-07-22 | 巴斯夫欧洲公司 | 含硅烷化合物作为添加剂的聚氨酯粘合剂 |
US20130158159A1 (en) * | 2011-12-19 | 2013-06-20 | Momentive Performance Materials Inc. | Epoxy-containing polysiloxane oligomer compositions, process for making same and uses thereof |
CN104080870A (zh) * | 2011-12-19 | 2014-10-01 | 莫门蒂夫性能材料股份有限公司 | 含环氧基团的聚硅氧烷低聚物组合物、其制备方法及其用途 |
CN105814254A (zh) * | 2013-11-18 | 2016-07-27 | 莫梅特公司 | 金属化织物及其制造方法 |
CN107109114A (zh) * | 2014-12-26 | 2017-08-29 | Posco公司 | 耐黑变性和耐蚀性优异的无铬涂覆组合物及表面处理钢板 |
CN108463544A (zh) * | 2015-12-11 | 2018-08-28 | 博斯蒂克股份公司 | 涂覆工业生产线的清洁组合物 |
WO2018178165A1 (en) * | 2017-03-29 | 2018-10-04 | Sika Technology Ag | Water-based composition having improved mechanical properties |
CN109868107A (zh) * | 2017-12-01 | 2019-06-11 | 万华化学(宁波)有限公司 | 一种粘合剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
US20220315816A1 (en) | 2022-10-06 |
WO2021005018A1 (en) | 2021-01-14 |
EP3996919A1 (en) | 2022-05-18 |
EP3763525A1 (en) | 2021-01-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104769071B (zh) | 胶粘组合物在潮湿环境中提供粘合的用途 | |
US6908654B2 (en) | Laminate with a peelable top layer and a method of peeling off the top layer from the laminate | |
US6797764B2 (en) | Water-based adhesive | |
KR100849400B1 (ko) | 마이클 부가 반응의 촉진 방법 | |
JP3743574B2 (ja) | 乾式接着貼り合わせ用の改良された2成分型水性接着剤 | |
CN112961640B (zh) | 一种用作吸塑胶的聚氨酯胶膜及制备方法和应用 | |
CN104755573A (zh) | 与未涂布的铝质工具具有低粘附的反应性聚烯烃热熔粘合剂及其作为层合热熔胶的用途 | |
JPH0881671A (ja) | 二液型水性接着剤 | |
US20140329074A1 (en) | Reactive polyolefin hot-melt adhesive having low viscosity and use thereof for textile laminations | |
KR101047384B1 (ko) | 드라이 라미네이트용 수성접착제 조성물 및 그것을 이용한 적층체 | |
CN113227184A (zh) | 聚氨酯贴面膜 | |
EP2938688B1 (en) | Waterborne adhesives | |
TWI772398B (zh) | 具有抗熱性改進之水媒性乾燥層壓黏結劑 | |
JPH1081865A (ja) | 接着剤組成物 | |
CN114040955A (zh) | 单组分可热活化聚氨酯水基粘合剂组合物 | |
US12043710B2 (en) | Two-component, water-based lamination adhesive and use of the same to bond substrates and foams | |
TW201335301A (zh) | 水性接著劑 | |
CN110662814B (zh) | 水基粘着剂组合物 | |
CN111742028A (zh) | 制备涂覆有粘合剂的制品的方法 | |
JP2015113375A (ja) | 水性接着剤および積層体 | |
CN112266759B (zh) | 难粘柔性材料用反应性胶粘剂及其应用 | |
KR20220117748A (ko) | 물품모재에 부착하기 위한 부재 및 그 부착방법 | |
MXPA99002602A (en) | Water-based vacuum forming laminating adhesive |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |