WO2021110087A1 - 潜伏型单组份聚氨酯热熔胶及其制备方法与胶膜 - Google Patents

潜伏型单组份聚氨酯热熔胶及其制备方法与胶膜 Download PDF

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WO2021110087A1
WO2021110087A1 PCT/CN2020/133556 CN2020133556W WO2021110087A1 WO 2021110087 A1 WO2021110087 A1 WO 2021110087A1 CN 2020133556 W CN2020133556 W CN 2020133556W WO 2021110087 A1 WO2021110087 A1 WO 2021110087A1
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latent
hot melt
component polyurethane
polyurethane hot
melt adhesive
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PCT/CN2020/133556
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English (en)
French (fr)
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梁坤焕
欧阳效明
梁锋
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广东盈通新材料有限公司
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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
    • C09J11/02—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
    • 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
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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

Definitions

  • the invention relates to the field of polymer adhesives, in particular to a latent single-component polyurethane hot melt adhesive and a preparation method and adhesive film thereof.
  • Polyurethane is a fast-developing multifunctional polymer synthetic material. Due to the diversification of raw materials and the adjustability of molecular structure, it can be made into foam, elastomer, coating, hot melt adhesive and other products. Its use Extremely broad. In addition, by adjusting the raw materials and formula of polyurethane, it is possible to design various types of polyurethane hot melt adhesives suitable for bonding between various materials and for various purposes. Polyurethane hot melt adhesive has excellent flexibility, impact resistance, chemical resistance, and has particularly excellent low temperature resistance and abrasion resistance.
  • polyurethane hot melt adhesives can be divided into thermoplastic polyurethane elastomer hot melt adhesives and reactive polyurethane hot melt adhesives.
  • Hot melt adhesives are more and more used due to their fast bonding, high efficiency, non-polluting, non-toxic and other characteristics, but traditional thermoplastic polyurethane hot melt adhesives are generally composed of thermoplastic polyurethane materials, which are not heat resistant and easy to dissolve. For organic solvents, the bonding strength is not particularly high. Therefore, it is currently mainly used in products that do not require heat resistance and do not require high bonding strength.
  • Reactive polyurethane hot melt adhesive is a new type of adhesive developed on the basis of traditional thermoplastic polyurethane materials.
  • the purpose of the present invention is to provide a reactive latent one-component polyurethane hot-melt adhesive.
  • a reactive latent one-component polyurethane hot-melt adhesive By introducing closed NCO groups into the polyurethane resin, a highly crosslinked network and high cohesion are obtained.
  • Another purpose of the present invention is to provide a latent one-component polyurethane hot melt adhesive preparation method, the method is simple in process, low cost, high preparation efficiency, and has prospects in industrial production; the present invention also Provide latent one-component polyurethane adhesive film cured by latent one-component polyurethane hot melt adhesive, with good initial adhesion, excellent final adhesion, storage stability; can be widely used in woodworking, textiles, outdoor clothing, Automobile, electronics, home appliances and other industries.
  • a latent one-component polyurethane hot-melt adhesive including the following components by weight percentage:
  • the polyurethane resin is selected from water-based polyurethane resins or solvent-based polyurethane resins.
  • the groups in the polyurethane resin include one or more of a hydroxyl group, a carboxyl group, and an amine group.
  • the group in the polyurethane resin includes a hydroxyl group, and the hydroxyl group is a terminal hydroxyl group.
  • the water-based polyurethane resin is selected from one or more of the following water-based polyurethane resins: Dispercoll U series from Covestro, such as U42, U48, U54, U58, U XP2612, U8755, U2849, U2815; Qingdao Yutian Chemical's water-based polyurethane, such as S906, S915, V216; Taiwan Coating's water-based polyurethane, such as 6010, 6045, 1030, 1045.
  • the above waterborne polyurethane resin has a hydroxyl-terminated structure.
  • the solvent-based polyurethane resin is selected from one or more of the following solvent-based polyurethane resins: Polyurethane resins for fabrics/fibers of Taiwan Coating, such as A2060, CX6080, CX6049, CX6030, NC5309, 2550; Qingdao Yutian Polyurethane resin for chemical leather, such as 7035 and 1050.
  • the polyurethane resin is selected from water-based polyurethane resins.
  • the polyurethane resin may also be selected from a mixture of crystalline polyurethane resins and amorphous polyurethane resins.
  • the crystalline polyurethane resin can improve the initial bonding strength and final bonding strength of the polyurethane hot melt adhesive.
  • the amorphous polyurethane resin under the joint action of other components, the wettability of the reactive polyurethane hot melt adhesive to the bonding substrate can be improved, thereby improving the bonding performance to the material.
  • the blocked curing agent is a blocked isocyanate curing agent;
  • the blocking agent for blocking the blocked curing agent is selected from the group consisting of hydroxyl type blocking agent, imine type blocking agent, active methylene type One or more of the blocking agents.
  • the hydroxyl type blocking agent may be further selected from phenolic blocking agents and alcohol blocking agents; the imine type blocking agent may be further selected from oxime blocking agents and lactam blocking agents; active methylene type blocking agents The agent may further be selected from diethyl malonate-based blocking agents and acetylacetone-based blocking agents.
  • the NCO group content of the closed curing agent is 2%-20%; further preferably 7-15%.
  • the NCO group content of the blocking curing agent has a very important relationship with the quality of the product.
  • too many NCO groups will produce a large number of bubbles during use, which is not conducive to bonding, and easily leads to the storage instability of the closed curing agent/polyurethane hot melt adhesive.
  • the deblocking temperature of the enclosed curing agent is 90-140°C.
  • the unblocking temperature of the blocking curing agent depends on the structure of the isocyanate and the type of blocking agent. The lower the unsealing temperature, the easier the unsealing, the shorter the time required, and the higher the use temperature, the shorter the unsealing time. Generally, the lower the unsealing temperature, the better, but it should not be too low. It is required that the sealed polyurethane prepared should be quite stable during storage and be convenient for transportation and operation.
  • the enclosed curing agent used in the present invention has a suitable unsealing temperature, and can be quickly unsealed when the unsealing temperature is reached, so as to cure the coating or adhesive layer.
  • the enclosed curing agent selects one or more of the following enclosed curing agents: the enclosed curing agent of Covestro of the United States, such as 2794, 2706, 2867, BL3175, BL3370; the enclosed curing agent of Mitsui Japan Agent, such as G282; Bathington's closed curing agent, such as 7982; Evonik Degussa's closed curing agent, such as B1358/100, B1370.
  • the enclosed curing agent of Covestro of the United States such as 2794, 2706, 2867, BL3175, BL3370
  • the enclosed curing agent of Mitsui Japan Agent such as G282
  • Bathington's closed curing agent such as 7982
  • Evonik Degussa's closed curing agent such as B1358/100, B1370.
  • the promoter is one or more of organotin catalysts, ammonia catalysts, and organobismuth catalysts.
  • the organotin catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, or organotin catalyst B8; one or more of the organic bismuth catalysts Bi2, Bi5, or Bi8; and ammonia-based catalysts are selected From triethylenediamine or N,N-dimethylcyclohexylamine.
  • the catalyst can reduce the activation energy required for the deblocking reaction to lower the deblocking temperature, which is beneficial to the rapid progress of the deblocking reaction.
  • the auxiliary agent is selected from one or two of antioxidants and ultraviolet absorbers.
  • the antioxidant is selected from one or two of hindered phenol antioxidants and phosphite antioxidants; the ultraviolet absorber is selected from benzophenone ultraviolet absorbers, benzene One or more of triazole ultraviolet absorbers and hindered amine ultraviolet absorbers.
  • the antioxidant may be selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, antioxidant TPP, and antioxidant B215;
  • the ultraviolet absorber may be selected from One or more of ultraviolet absorber UV-9, ultraviolet absorber UV-328, ultraviolet absorber UV-5411, ultraviolet absorber UV-622, ultraviolet absorber UV-B2500, and ultraviolet absorber UV-P.
  • an antioxidant and an ultraviolet absorber are added to improve the heat-resistant, anti-oxidant and yellowing resistance of the polyurethane hot melt adhesive.
  • the method for preparing the latent one-component polyurethane hot melt adhesive includes the following steps:
  • the polyurethane resin, closed curing agent, accelerator and auxiliary agent are mixed uniformly to obtain latent one-component polyurethane hot melt adhesive.
  • An adhesive film obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive.
  • the latent one-component polyurethane hot-melt adhesive is added to a coating machine, and the scraper of the coating head is applied to the glassine paper according to the specified thickness to obtain an adhesive film of the specified thickness.
  • the thickness of the latent one-component polyurethane hot melt adhesive coating is not less than 0.03 mm;
  • the latent one-component polyurethane hot melt adhesive coating should not be too thin.
  • the thinner the coating, the softer the polyurethane film, but the smaller the tear strength of the film, the thinner the contact layer with the adherend, and the bonding strength The worse; the coating becomes thicker, although the adhesive strength of the adhesive film is large, the heat absorption per unit area of the adhesive film increases, the unsealing reaction is not complete, and the adhesive film is easy to overflow due to the thickness of the adhesive. It is unsightly and has poor flexibility.
  • the present invention uses a blocked isocyanate curing agent to temporarily seal the active -NCO groups in the polyurethane resin, and when used, the blocked curing agent is unblocked under heating conditions of 130-160°C to release the active -NCO groups It reacts with the hydroxyl in the polyurethane resin, the moisture in the air or on the adherend, or the active hydrogen substance to form a partially cross-linked structure to improve the product's bonding strength, heat resistance, hydrolysis resistance and other properties;
  • the active -NCO group of the present invention is temporarily encapsulated in the polyurethane resin, so it has the characteristic of "latency", which effectively avoids the shortcomings of harsh storage conditions and slow post-curing of reactive polyurethane hot melt adhesives;
  • the polyurethane hot melt adhesive preparation method of the present invention has simple process, low cost, high preparation efficiency, and has a prospect in industrial production;
  • the adhesive film obtained by curing the latent one-component polyurethane of the present invention has good initial adhesion, excellent final adhesion, and storage stability; it can be widely used in woodworking, textiles, outdoor clothing, automobiles, electronics, Home appliances and other industries.
  • a latent one-component polyurethane hot-melt adhesive including the following components by weight percentage:
  • the method for preparing the latent one-component polyurethane hot melt adhesive includes the following steps:
  • the temperature is 130°C
  • dibutyltin dilaurate, antioxidant 1010, and ultraviolet absorber UV-328 are put into the reactor and mixed uniformly at a low speed at a stirring speed of 100 rpm to obtain a latent one-component polyurethane hot melt adhesive.
  • An adhesive film obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive.
  • the latent one-component polyurethane hot melt adhesive is added to the coating machine, and the coating head is coated on the glassine paper with a thickness of 0.08 mm by the doctor blade of the coating head to obtain an adhesive film.
  • a latent one-component polyurethane hot-melt adhesive including the following components by weight percentage:
  • the method for preparing the latent one-component polyurethane hot melt adhesive includes the following steps:
  • An adhesive film obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive.
  • the latent one-component polyurethane hot melt adhesive is added to the coating machine, and the coating head is coated on the glassine paper with a thickness of 0.1 mm by the doctor blade of the coating head to obtain an adhesive film.
  • a latent one-component polyurethane hot-melt adhesive including the following components by weight percentage:
  • the method for preparing the latent one-component polyurethane hot melt adhesive includes the following steps:
  • the solvent-based polyurethane resin CX6049, solvent-based polyurethane resin 2550, closed curing agent B1358/100 (NCO group content of 12.5%, unblocking temperature 130 °C), triethylene diamine, antioxidant 168, ultraviolet absorber UV -9 is put into the reaction kettle and mixed uniformly at a low speed at a stirring speed of 100 rpm to obtain a latent one-component polyurethane hot melt adhesive.
  • An adhesive film obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive.
  • the latent one-component polyurethane hot melt adhesive is added to the coating machine, and the coating head is coated on the glassine paper with a thickness of 0.05 mm by the doctor blade of the coating head to obtain an adhesive film.
  • a latent one-component polyurethane hot-melt adhesive including the following components by weight percentage:
  • the method for preparing the latent one-component polyurethane hot melt adhesive includes the following steps:
  • An adhesive film obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive obtained by curing the above-mentioned latent single-component polyurethane hot melt adhesive.
  • the latent one-component polyurethane hot-melt adhesive is added to the coating machine, and the coating head is coated on the glassine paper with a thickness of 0.15 mm by the doctor blade of the coating head to obtain an adhesive film.
  • a polyurethane adhesive including the following components by weight percentage:
  • the preparation method of the above polyurethane adhesive includes the following steps:
  • solvent-based polyurethane resin CX6049, solvent-based polyurethane resin 2550, curing agent CA-800D (NCO group content of 13%, non-closed type), antioxidant 168, and ultraviolet absorber UV-9 into the reactor, Mix uniformly at a low speed at a stirring speed of 100 rpm to obtain a polyurethane adhesive.
  • the above-mentioned polyurethane adhesive is added to the coating machine, and the coating head is coated on the glassine paper with a thickness of 0.10 mm by the doctor blade of the coating head, and cured to obtain an adhesive film.
  • the test method is as follows:
  • Peeling strength on the laminating machine, press 150 degrees for 40 seconds on the bonding part, (bonding structure: high tear strength Oxford cloth/adhesive film/aluminum or ABS/adhesive film/aluminum bonding) , After cooling, test its peel strength.
  • Storage period Expose the film or glue to the air according to the normal packaging method without isolating the air. After 4 months of storage, take a sample and press it at 150°C for 40 seconds on the laminating machine.
  • the adhesive structure is high-tear. Bonding of oxford cloth with crack strength to aluminum sheet, and test its peel strength after cooling.
  • the latent polyurethane adhesive film prepared by the present invention has good initial adhesion and storage stability, effectively avoids the shortcomings of harsh storage conditions and slow post-curing of reactive polyurethane hot melt adhesives, and has excellent Ultimate adhesion; can be widely used in woodworking, textiles, outdoor clothing, automobiles, electronics, home appliances and other industries.

Abstract

一种潜伏型单组份聚氨酯热熔胶及其制备方法与胶膜，涉及高分子胶粘剂领域。该潜伏型单组份聚氨酯热熔胶，包括按重量百分比计的以下组分：聚氨酯树脂70％-95％；封闭型固化剂4.8％-29.3％；促进剂0.01％-0.2％；助剂0.01％-0.5％。所述潜伏型单组份聚氨酯热熔胶具有良好的粘接强度、耐热、耐水解性等性能；制备方法工艺简单、成本低廉、制备效率高，在工业化生产中具有前景；由潜伏型单组份聚氨酯热熔胶固化得到的潜伏型单组份聚氨酯胶膜，具有良好的初粘性、优秀的终粘力、贮存稳定性；可广泛用于木工、纺织、户外服装、汽车、电子、家电等行业。

Description

[根据细则37.2由ISA制定的发明名称]　潜伏型单组份聚氨酯热熔胶及其制备方法与胶膜 技术领域
本发明涉及高分子胶粘剂领域，特别是一种潜伏型单组份聚氨酯热熔胶及其制备方法与胶膜。
背景技术
聚氨酯是一种发展迅速的多功能性高分子合成材料，由于原料品种的多样化及分子结构的可调节性，可以制成泡沫塑料、弹性体、涂料、热熔胶等多种产品，其用途极其广泛。此外，通过调节聚氨酯的原料和配方，可以设计出适合各种材料间的粘结、各种不同用途的多种类型聚氨酯热熔胶。聚氨酯热熔胶具有优良的柔韧性、耐冲击性、耐化学药品性，并且具有特别优异的耐低温性能和耐磨性。
聚氨酯热熔胶按固化形式不同可分为热塑性聚氨酯弹性体热熔胶和反应性聚氨酯热熔胶。热熔胶因其粘接快速、效率高、不污染、无毒等特性而得到越来越多的应用，但传统的热塑性聚氨酯热熔胶一般是由热塑性聚氨酯物质构成，不耐热、易溶于有机溶剂、粘接强度也不是特别高，因此，目前主要应用于无需耐热和粘接强度要求不高的产品中。反应性聚氨酯热熔胶是在传统热塑性聚氨酯材料基础上发展起来的一类新型胶粘剂，具有定位快、粘接强度高、拉伸强度高、弹性优良、耐磨、耐油和耐寒等优点，广泛用于电子、木材加工、汽车等行业。但是由于其具有反应性异氰酸酯(-NCO)基团，所以储存条件苛刻(低温、隔绝湿气，一般情况下抽真空储存)，而且后固化需要3-7天，限制了其在一些快速使用领域的应用。
因此，有必要开发一种可以在常规条件下稳定贮存、且具有反应性的潜伏型单组份聚氨酯热熔胶以及由其固化得到的胶膜。
发明内容
针对现有技术的不足，本发明的目的在于提供一种具有反应性的潜伏型单组份聚氨酯热熔胶，通过在聚氨酯树脂中引入封闭的NCO基团，得到具有高度交联网络及内聚力大的结构性胶粘剂；本发明的另一个目的在于提供一种潜伏型单组份聚氨酯热熔胶的制备方法，该方法工艺简单、成本低廉、制备效率高，在工业化生产中具有前景；本发明还提供由潜伏型单组份聚氨酯热熔胶固化得到的潜伏型单组份聚氨酯胶膜，具有良好的初粘性、优秀的终粘力、贮存稳定性；可广泛用于木工、纺织、户外服装、汽车、电子、家电等行业。
本发明采用以下技术方案：
一种潜伏型单组份聚氨酯热熔胶，包括按重量百分比计的以下组分：
Figure PCTCN2020133556-appb-000001
优选地，所述聚氨酯树脂选自水性聚氨酯树脂或溶剂型聚氨酯树脂。
优选地，所述聚氨酯树脂中的基团包括羟基、羧基、胺基中的一种或多种。
进一步优选地，所述聚氨酯树脂中的基团包括羟基，所述羟基为端羟基。
具体地，所述水性聚氨酯树脂选自以下水性聚氨酯树脂中的一种或多种：美国科思创的Dispercoll U系列，例如U42、U48、U54、U58、U XP2612、U8755、U2849、U2815；青岛宇田化工的水性聚氨酯，例如S906、S915、V216；台湾高鼎的水性聚氨酯，例如6010、6045、1030、1045。以上水性聚氨酯树脂具有端羟基结构。
具体地，所述溶剂型聚氨酯树脂选自以下溶剂型聚氨酯树脂中的一种或多种：台湾高鼎的织物/纤维用聚氨酯树脂，例如A2060、CX6080、CX6049、CX6030、NC5309、2550；青岛宇田化工的革用聚氨酯树脂，例如7035、1050。
进一步优选地，所述聚氨酯树脂选自水性聚氨酯树脂。
本发明中，所述聚氨酯树脂还可以选自结晶性聚氨酯树脂和无定型聚氨酯树脂混合物。
本发明中，结晶性聚氨酯树脂可以提高聚氨酯热熔胶的初期粘结强度和最终粘结强度。同时，配合无定型聚氨酯树脂，在其他组分共同作用下，可以提高反应型聚氨酯热熔胶对粘结基材的浸润性，从而提高对材料的粘结性能。
优选地，所述封闭型固化剂为封闭型异氰酸酯固化剂；对所述封闭型固化剂进行封闭的封闭剂选自羟基型的封闭剂、亚胺基型的封闭剂、活泼亚甲基型的封闭剂中的一种或多种。
具体地，羟基型的封闭剂进一步可以选自酚类封闭剂、醇类封闭剂；亚胺基型的封闭剂进一步可以选自肟类封闭剂、内酰胺类封闭剂；活泼亚甲基型封闭剂进一步可以选自丙二酸二乙酯类封闭剂、乙酰丙酮类封闭剂。
优选地，所述封闭型固化剂的NCO基团含量为2％-20％；进一步优选为7-15％。
本发明中，封闭固化剂的NCO基团含量对产品的品质具有十分重要的关系。NCO基团含量越高，意味着活性NCO基团越多，解封后的NCO基团与基材表面含有微量水分或其他含活泼氢的化合物发生化学交联的反应越多，从而使其生成具有高度交联网络结构及内聚力大的氨基甲酸酯基的成份越多，有利于提高产品的粘接性能。然而NCO基团过多会在使用中产生大量汽泡，不利于粘接，且容易导致封闭型固化剂/聚氨酯热熔胶的贮存不稳定。
优选地，所述封闭型固化剂解封温度为90-140℃。
封闭型固化剂的解封温度取决于异氰酸酯的结构、封闭剂种类。解封温度越低，越容易解封，所需时间越短，使用温度越高，解封时间越短。一般地，解封温度越低越好，但不能太低，要求所制备的封闭型聚氨酯在贮存过程中需相当稳定，便于运输和操作。本发明中所采用的封闭型固化剂具有合适的解封温度，在达到解封温度时能快速解封，以使涂层或胶层固化。
具体地，所述封闭型固化剂选择以下封闭型固化剂中的一种或多种：美国科思创的封闭型固化剂，例如2794、2706、2867、BL3175、BL3370；日本三井的封闭型固化剂，例如G282；巴辛顿的封闭型固化剂，例如7982；赢创德固赛的封闭型固化剂，例如B1358/100、B1370。
优选地，所述促进剂为有机锡催化剂、氨类催化剂、有机铋催化剂中的一种或多种。
具体地，有机锡催化剂选自二月桂酸二丁基锡、辛酸亚锡或有机锡催化剂B8中的一种或多种；有机铋催化剂Bi2、Bi5或Bi8中的一种或多种；氨类催化剂选自三乙烯二胺或N,N-二甲基环己胺。
本发明中，催化剂能降低解封闭反应所需要的活化能来降低解封温度，有利于解封反应的快速进行。
优选地，所述助剂选自抗氧剂和紫外线吸收剂中的一种或两种。
进一步优选地，所述抗氧剂选自受阻酚类抗氧剂和亚磷酸酯类抗氧剂中的一种或两种；所述紫外线吸收剂选自二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂和受阻胺类紫外线吸收剂中的一种或多种。
具体地，所述抗氧剂可选自抗氧化剂1010、抗氧剂1076、抗氧剂168、抗氧剂TPP、抗氧剂B215中的一种或多种；所述紫外线吸收剂可选自紫外线吸收剂UV-9、紫外线吸收剂UV-328、紫外线吸收剂UV-5411、紫外线吸收剂UV-622、紫外线吸收剂UV-B2500、紫外线吸收剂UV-P中的一种或多种。
本发明中，加入抗氧剂和紫外线吸收剂，提高了聚氨酯热熔胶的耐热抗氧化性能和耐黄变的性能。
上述的潜伏型单组份聚氨酯热熔胶的制备方法，包括以下步骤：
将聚氨酯树脂、封闭型固化剂、促进剂、助剂混合均匀，即得到潜伏型单组份聚氨酯热熔胶。
一种胶膜，由上述的潜伏型单组份聚氨酯热熔胶固化得到。
具体地，将所述潜伏型单组份聚氨酯热熔胶加入到涂布机中，由涂布头的刮刀按规定的厚度涂布在格拉辛纸上，得到规定厚度的胶膜。
优选的，潜伏型单组份聚氨酯热熔胶涂层的厚度不小于0.03毫米；
潜伏型单组份聚氨酯热熔胶涂层不宜太薄，涂层越薄，聚氨酯胶膜越柔软，但胶膜的抗撕裂强度越小，与被粘物的接触层越薄，粘接强度越差；涂层变厚，虽然胶膜的粘接强度大，但胶膜的单位面积的吸热量增加，解封反应不够完全，且胶膜在粘接物上因胶厚易溢边，不美观，柔软性变差。
本发明的有益效果
(1)本发明采用封闭型异氰酸酯固化剂将活性的-NCO基团暂时封闭在聚氨酯树脂中，使用时在130-160℃加热条件下将封闭固化剂解封，释放出活泼的-NCO基团与聚氨酯树脂中的羟基、空气中或被粘物上的水分或活泼氢物质反应而形成部分交联网状结构，来提高产品的粘接强度、耐热、耐水解性等性能；
(2)本发明的活性的-NCO基团暂时封存在聚氨酯树脂中，因此具有“潜伏”的特点，有效地避免了反应型聚氨酯热熔胶储存条件苛刻和后固化慢的缺点；
(3)本发明的聚氨酯热熔胶制备方法工艺简单、成本低廉、制备效率高，在工业化生产中具有前景；
(4)由本发明的潜伏型单组份聚氨酯固化而得到的胶膜，具有良好的初粘性、优秀的终粘力、贮存稳定性；可广泛用于木工、纺织、户外服装、汽车、电子、家电等行业。
具体实施方式
实施例1
一种潜伏型单组份聚氨酯热熔胶，包括按重量百分比计的以下组分：
Figure PCTCN2020133556-appb-000002
上述的潜伏型单组份聚氨酯热熔胶的制备方法，包括以下步骤：
将水性聚氨酯树脂U42、水性聚氨酯树脂U58、封闭型固化剂2794(NCO基团含量为11.5％、解封温度105℃)、封闭型固化剂B1358/100(NCO基团含量为12.5％、解封温度130℃)、二月桂酸二丁基锡、抗氧剂1010、紫外线吸收剂UV-328投入到反应釜中，在100rpm的搅拌速度下低速混合均匀，即得到潜伏型单组份聚氨酯热熔胶。
一种胶膜，由上述的潜伏型单组份聚氨酯热熔胶固化得到。
具体地，将潜伏型单组份聚氨酯热熔胶加入到涂布机中，由涂布头的刮刀按0.08mm厚度涂布在格拉辛纸上，得到胶膜。
实施例2
一种潜伏型单组份聚氨酯热熔胶，包括按重量百分比计的以下组分：
Figure PCTCN2020133556-appb-000003
上述的潜伏型单组份聚氨酯热熔胶的制备方法，包括以下步骤：
将水性聚氨酯树脂U2849、水性聚氨酯树脂U58、封闭型固化剂B1358/100(NCO基团含量为12.5％、解封温度130℃)、辛酸亚锡、抗氧剂1010、紫外线吸收剂UV-5411投入到反应釜中，在50rpm的搅拌速度下低速混合均匀，即得到潜伏型单组份聚氨酯热熔胶。
一种胶膜，由上述的潜伏型单组份聚氨酯热熔胶固化得到。
具体地，将潜伏型单组份聚氨酯热熔胶加入到涂布机中，由涂布头的刮刀按0.1mm厚度涂布在格拉辛纸上，得到胶膜。
实施例3
一种潜伏型单组份聚氨酯热熔胶，包括按重量百分比计的以下组分：
Figure PCTCN2020133556-appb-000004
上述的潜伏型单组份聚氨酯热熔胶的制备方法，包括以下步骤：
将溶剂型聚氨酯树脂CX6049、溶剂型聚氨酯树脂2550、封闭型固化剂B1358/100(NCO基团含量为12.5％、解封温度130℃)、三乙烯二胺、抗氧剂168、紫外线吸收剂UV-9投入到反应釜中，在100rpm的搅拌速度下低速混合均匀，即得到潜伏型单组份聚氨酯热熔胶。
一种胶膜，由上述的潜伏型单组份聚氨酯热熔胶固化得到。
具体地，将潜伏型单组份聚氨酯热熔胶加入到涂布机中，由涂布头的刮刀按0.05mm厚度涂布在格拉辛纸上，得到胶膜。
实施例4
一种潜伏型单组份聚氨酯热熔胶，包括按重量百分比计的以下组分：
Figure PCTCN2020133556-appb-000005
上述的潜伏型单组份聚氨酯热熔胶的制备方法，包括以下步骤：
将溶剂型聚氨酯树脂A2060、溶剂型聚氨酯树脂7035、封闭型固化剂BL3175(NCO基团含量为11％、解封温度120℃)、有机锡催化剂B8、抗氧剂1010、紫外线吸收剂UV-P投入到反应釜中，在150rpm的搅拌速度下低速混合均匀，即得到潜伏型单组份聚氨酯热熔胶。
一种胶膜，由上述的潜伏型单组份聚氨酯热熔胶固化得到。
具体地，将潜伏型单组份聚氨酯热熔胶加入到涂布机中，由涂布头的刮刀按0.15mm厚度涂布在格拉辛纸上，得到胶膜。
对比例1
一种聚氨酯胶粘剂，包括按重量百分比计的以下组分：
Figure PCTCN2020133556-appb-000006
上述的聚氨酯胶粘剂的制备方法，包括以下步骤：
将溶剂型聚氨酯树脂CX6049、溶剂型聚氨酯树脂2550、固化剂CA-800D(NCO基团含量为13％、非封闭型)、抗氧剂168、紫外线吸收剂UV-9投入到反应釜中，在100rpm的搅拌速度下低速混合均匀，即得到聚氨酯胶粘剂。
将上述的聚氨酯胶粘剂加入到涂布机中，由涂布头的刮刀按0.10mm厚度涂布在格拉辛纸上，固化得到胶膜。
实验例1
对实施例1-4制备的胶膜、对比例1的胶膜以及市售的胶膜(美国SRT-3415，羟基聚氨酯)、反应聚氨酯(美国EH9650，端NCO基湿固化型反应聚氨酯)进行性能测定，结果如下表1所示。
测试方法如下：
1)剥离强度：在压合机上，用150度压40秒于粘接件，(粘接结构为：高撕裂强度的牛津布/胶膜/铝或ABS/胶膜/铝的粘接)，冷却后，检测其剥离强度。
2)初粘性：在压合机上压合粘接结构的物件，冷却90分钟后检测其剥离强度。
3)终粘强度：将粘接结构为高撕裂强度的牛津布/铝片的粘接件放置于70℃、95％湿度的恒温恒湿老化箱中加速老化相应时间，取样、冷却后测试剥离强度。
4)贮存期：将胶膜或胶水按正常的包装方式暴露于空气中，不隔绝空气，贮放4个月后，取样，在压合机上用150度压40秒，粘接结构为高撕裂强度的牛津布对铝片的粘接，冷却后检测其剥离强度。
5)耐温性：将粘接结构为高撕裂强度的牛津布/铝片的粘接件放置100℃烘箱中老化10天后，于50℃的恒温拉力机中测试其剥离强度，大于40N/25mm为通过，小于40N/25mm则为不通过。
表1胶膜的性能
Figure PCTCN2020133556-appb-000007
Figure PCTCN2020133556-appb-000008
注：标识为布断裂或破坏ABS，是指剥离强度达到该数值时，粘接材料已被破坏。
从表1可以看出，由本发明制备的潜伏型聚氨酯胶膜具有良好的初粘性、贮存稳定性，有效地避免了反应型聚氨酯热熔胶储存条件苛刻和后固化慢的缺点，并有优秀的最终粘接力；可广泛用于木工、纺织、户外服装、汽车、电子、家电等行业。

Claims (10)

  1. 一种潜伏型单组份聚氨酯热熔胶，其特征在于，包括按重量百分比计的以下组分：
    Figure PCTCN2020133556-appb-100001
  2. 根据权利要求1所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述聚氨酯树脂选自水性聚氨酯树脂或溶剂型聚氨酯树脂。
  3. 根据权利要求1或2所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述聚氨酯树脂中的基团包括羟基、羧基、胺基中的一种或多种。
  4. 根据权利要求1所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述封闭型固化剂为封闭型异氰酸酯固化剂；对所述封闭型固化剂进行封闭的封闭剂选自羟基型的封闭剂、亚胺基型的封闭剂、活泼亚甲基型的封闭剂中的一种或多种。
  5. 根据权利要求1或4所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述封闭型固化剂的NCO基团含量为2％-20％，解封温度为90-140℃。
  6. 根据权利要求1所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述促进剂为有机锡催化剂、氨类催化剂、有机铋催化剂中的一种或多种。
  7. 根据权利要求1所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述助剂选自抗氧剂和紫外线吸收剂中的一种或两种。
  8. 根据权利要求7所述的潜伏型单组份聚氨酯热熔胶，其特征在于，所述抗氧剂选自受阻酚类抗氧剂和亚磷酸酯类抗氧剂中的一种或两种；所述紫外线吸收剂选自二苯甲酮类紫外线吸收剂、苯并三唑类紫外线吸收剂和受阻胺类紫外线吸收剂中的一种或多种。
  9. 根据权利要求1-8中任一项所述的潜伏型单组份聚氨酯热熔胶的制备方法，其特征在于，包括以下步骤：
    将聚氨酯树脂、封闭型固化剂、促进剂、助剂混合均匀，即得到潜伏型单组份聚氨酯热熔胶。
  10. 一种胶膜，其特征在于，由权利要求1-8中任一项所述的潜伏型单组份聚氨酯热熔胶固化得到。
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