WO2024037170A1 - 一种hdi/ipdi固化剂、制备方法、用途及热固化pu胶膜 - Google Patents

一种hdi/ipdi固化剂、制备方法、用途及热固化pu胶膜 Download PDF

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WO2024037170A1
WO2024037170A1 PCT/CN2023/100964 CN2023100964W WO2024037170A1 WO 2024037170 A1 WO2024037170 A1 WO 2024037170A1 CN 2023100964 W CN2023100964 W CN 2023100964W WO 2024037170 A1 WO2024037170 A1 WO 2024037170A1
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curing agent
hdi
parts
film
ipdi
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PCT/CN2023/100964
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English (en)
French (fr)
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刘卓立
李彪
朱晓亮
文德兴
韦继炜
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李彪
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    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to a protective film base material, in particular to an HDI/IPDI curing agent, preparation method, use and thermal curing PU adhesive film.
  • the protective film is a layer of adhesive film that fits on the surface of the physical object to be protected.
  • the usual structure is upper protective film + functional coating + protective film base material + silicone layer + release film.
  • protective film base materials on the market include PET (polyethylene terephthalate) film, TPU (thermoplastic polyurethane) film, PVC (polyvinyl chloride) film, PE (polyethylene) film, OPP (polypropylene) ) film, as well as some high-end high-temperature films such as PI (polyimide) film, PEN (polyethylene naphthalate) film and PEEK (polyetheretherketone) film, etc.
  • TPU film is a type of polyurethane that can be plasticized by heating and dissolved by solvent. It mainly uses an extruder to mix, melt and plasticize, extrusion and cast, and cool and shape TPU rubber particles at a temperature of about 200°C. Finished film. Because polyurethane is a block polymer composed of isocyanate hard segments and polyol soft segments, which has both plasticity and elasticity. It has a wide adjustable range of hardness and elasticity, and has excellent wear resistance, weather resistance and chemical resistance. , so it is widely used in the fields of electronics, medical care, construction, building materials, and aerospace.
  • TPU has gradually replaced soft PVC as the more commonly used protective film base material
  • its complex casting and extrusion process and high-temperature plasticization can easily cause the film to yellow, affecting transparency and poor haze, which limits its application scenarios.
  • thermoplastic TPU direct-coated silicone is easily swollen and whitened by solvents, and the small molecule plasticizer in it can easily deactivate the platinum catalyst in the silicone. It needs to be fitted with an intermediate isolation layer, which increases the process difficulty and cost of the protective film manufacturing end.
  • TPU film needs to be plasticized at a high temperature of about 200°C during cast extrusion, which can easily cause the film to yellow and cannot be used in fields with high requirements for transparency and haze; and there is no intermolecular between thermoplastic TPU molecules.
  • Forming a cross-linked network, directly coating silica gel will swell and turn white due to the solvent in it, and the small molecule plasticizer in it can easily deactivate the platinum catalyst in the silica gel, making the silica gel unable to solidify.
  • an intermediate isolation layer such as PET film
  • Thermoset TPU adhesive film is formed by optimizing and improving the formula of PU coating. It has insufficient leveling properties. Most of the existing isocyanate curing agents have high viscosity and are prone to poor leveling, bubble spots and orange peel. Problems such as this can generally be improved by lowering the construction viscosity, but this cannot be applied thickly, which limits the scope of application.
  • the patent application number CN110431173A discloses a method for preparing a thermoplastic polyurethane film, which is characterized in that the preparation method includes preparing a polyurethane resin composition including a polyurethane resin, a first isocyanate-based curing agent and an organic solvent; by adding The polyurethane resin composition is applied to a base film and the polyurethane resin composition is heat-treated to prepare a laminate including a polyurethane resin layer; two laminates are provided to be joined such that the respective polyurethanes of the laminate The resin layers are opposed to each other; and a thermoplastic polyurethane film including two polyurethane resin layers in direct contact with each other is formed by aging of the joined laminate.
  • thermoplastic polyurethane film has the advantage that a thermoplastic polyurethane film with large thickness and excellent durability can be easily produced.
  • this preparation method mainly prepares polyurethane films by laminating two sides, it has shortcomings such as poor recoatability, difficult construction, and high requirements on the interface bonding strength range of the polyurethane resin layer.
  • the patent application number CN114149781A discloses a method for preparing a protective film from TPU composite glue. It is characterized in that the existing TPU particles are modified by using aliphatic polyurethane acrylic resin and ketone-aldehyde resin to improve the hardness and modulus of the TPU glue layer formed after the obtained TPU composite glue is cured, which can be used as a coating soft film layer Provides acupressure rebound effect.
  • the design idea of this patent is close to that of the present invention, but because it cannot be directly coated with silicone, it is only equivalent to an improved mechanical performance structure of the TPU layer. It requires a multi-layer structure, has tedious construction steps, and has shortcomings such as a narrow adjustment range.
  • the existing technology has the following shortcomings:
  • Ordinary thermosetting PU adhesive film has low construction solid content, poor leveling when thickly coated, prone to bubble spots, orange peel, and shrinkage of the edges without the base material, making it difficult to form a film.
  • the traditional TPU film’s cast extrusion process is complex and high-temperature plasticization can easily cause the film to turn yellow, affecting transparency and haze, which limits its application scenarios.
  • Thermoplastic TPU direct-coated silicone is easily swollen and whitened by solvents, or directly deactivates the platinum catalyst in the silicone, making the silicone unable to solidify. It needs to be fitted with an intermediate isolation layer, which increases the process difficulty and cost of the protective film manufacturing end.
  • Ordinary thermosetting PU adhesive film itself does not have the functions of anti-fingerprint, slippery, and high water drop angle.
  • the protective film manufacturing end needs to be coated with a functional coating to achieve the functions of anti-fingerprint, slippery, and high water drop angle, which increases protection.
  • the construction cost at the membrane manufacturing end and the construction process are complex.
  • the present invention provides an HDI/IPDI curing agent, preparation method, use and thermal curing PU adhesive film.
  • An HDI/IPDI curing agent made of ester solvent, trimethylolpropane, hexamethylene diisocyanate, isophorone diisocyanate and dibutyltin dilaurate.
  • the molar ratio between the hexamethylene diisocyanate, isophorone diisocyanate and trimethylolpropane is (2.0 - 3.0): (1.2 - 1.8): (0.8 - 1. 2).
  • the weight percentage of dibutyltin dilaurate is 0.03-0.08 %.
  • the ester solvent is butyl acetate or ethyl acetate.
  • a method for preparing the HDI/IPDI curing agent as described above the steps are as follows: in a four-necked flask equipped with a stirrer, a condenser, and a thermometer, add the above-mentioned ester solvent, trimethylolpropane (TMP), and hexafluoroethylene Methylene diisocyanate (HDI) and isophorone diisocyanate (IPDI) are heated to 80°C while stirring, and then the insulation reaction is carried out. During the insulation reaction, dibutyltin dilaurate (DBTDL) is added in 3 to 5 times. , react for 2.5-3h until the insoluble substances in the system disappear, and obtain the HDI/IPDI curing agent.
  • TMP trimethylolpropane
  • HDI hexafluoroethylene Methylene diisocyanate
  • IPDI isophorone diisocyanate
  • DBTDL dibutyltin dilaurate
  • the HDI/IPDI curing agent is used to prepare a protective film.
  • the PU adhesive film includes the following raw materials in parts by weight: 30-50 parts of hydroxyl resin, 0.1-0.2 parts of leveling agent, and ultraviolet rays 2 - 4 parts of absorbent, 20 - 40 parts of solvent, 5 - 10 parts of small molecular weight polycaprolactone glycol, 0.1 - 0.5 parts of hand smooth agent, 1 - 3 parts of anti-graffiti agent, hydrophobic agent 1-3 parts, catalyst 0.01-1.5 parts and curing agent 15-40 parts; the curing agent is HDI/IPDI curing agent or hexamethylene diisocyanate trimer and HDI/IPDI curing agent in any proportion Compositions.
  • the hydroxy resin is one or a combination of two or more of hydroxy acrylic resin, polyester, polyether, epoxy resin and polycarbonate;
  • the leveling agent is silicone modified polyether oxane, organic A combination of one or more of silicon-modified polyester polyol and silicone-modified polyacrylate;
  • the solvent is one or more of ester solvents, amide solvents and ether solvents Composition;
  • the catalyst is one of an organic bismuth catalyst and an organic tin catalyst.
  • a method for preparing the thermally cured PU adhesive film as described above, the steps are as follows:
  • the present invention uses trimethylolpropane combined with isophorone diisocyanate and hexamethylene diisocyanate to form an HDI/IPDI curing agent.
  • the cross-linked structure is closer than that of hexamethylene diisocyanate trimer and is self-made.
  • HDI/IPDI curing agent has lower viscosity and better leveling than traditional isocyanate curing agent. It can not only increase the construction solid content during coating, but also solve the problem of poor leveling when thick coating, prone to bubble spots, orange peel lines and Edge shrinkage and other problems, but also can effectively improve the hardness and toughness of PU film.
  • the PU glue produced by the HDI/IPDI curing agent of the present invention can be directly coated on the release film to form a film, replacing the traditional cast TPU process.
  • the production process is simple and efficient, and the glue film is white and transparent.
  • the heat-cured PU adhesive film produced by the present invention through HDI/IPDI curing agent has a cross-linked network formed between the molecules, has better mechanical properties, can be directly coated with silicone, has a simpler structure and is easy to construct, solving the problems of traditional thermoplastic TPU direct-coated silicone is easily swollen and whitened by solvents or directly deactivates the silicone catalyst, causing the silicone to fail to solidify.
  • the problem requires fitting an intermediate isolation layer, which reduces the process difficulty and cost of the protective film manufacturing end.
  • the heat-cured PU adhesive film of the present invention can achieve anti-fingerprint, slippery, and high water drop angle functions directly on the PU adhesive film by adding a smooth hand feel agent, an anti-graffiti agent, and a hydrophobic agent, thereby simplifying the original functional coating , reducing the construction cost at the manufacturing end of the protective film and making construction more convenient.
  • An HDI/IPDI curing agent consisting of butyl acetate (chemical formula: CH 3 COO(CH 2 ) 3 CH 3 ) or ethyl acetate (chemical formula C 4 H 8 O 2 ) or NMP (chemical formula C 5 H 9 NO), Trimethylolpropane (TMP, chemical formula: CH 3 CH 2 C(CH 2 OH) 3 ), hexamethylene diisocyanate (HDI, chemical formula: C 8 H 12 N 2 O 2 ), isophorone diisocyanate (IPDI, chemical formula: C 12 H 18 N 2 O 2 ) and dibutyltin dilaurate (DBTDL, molecular formula: C 32 H 64 O 4 Sn).
  • TMP Trimethylolpropane
  • HDI chemical formula: C 8 H 12 N 2 O 2
  • IPDI isophorone diisocyanate
  • DBTDL dibutyltin dilaurate
  • the synthesis method of the HDI/IPDI curing agent In a four-necked flask equipped with a stirrer, condenser, and thermometer, add measured amounts of butyl acetate, TMP, HDI, and IPDI respectively, and add an appropriate amount of catalyst DBTDL in multiple times, React for 3 hours at 80°C until the insoluble matter in the system disappears to obtain the HDI/IPDI curing agent. Recover the excess isocyanate and incorporate it into the next feed. Measure the mass fraction of -NCO groups in the system (theoretical NCO% is 18.26 %, the actual measurement is about 18.40%), and detect the viscosity of the reaction product at 25°C.
  • the polyurethane coating prepared using IPDI trimer has the characteristics of high hardness and high elastic modulus. However, because it is solid at room temperature, it is still highly viscous and difficult to apply even after dilution with solvents, and is inconvenient to construct.
  • the present invention uses Trihydric alcohol combines IPDI and HDI to form a trimer. The cross-linked structure is tighter than that of HDI trimer alone. It can prepare coatings with high hardness, high elastic modulus, high elongation at break and the ability to repeatedly coat silicone and smooth coatings. Cloth type soft film. By using different hydroxyl component A, the hardness can be a series of products ranging from Shore hardness 70A to Shore hardness 70D to meet different design needs.
  • a heat-curing PU adhesive film includes the following raw materials in parts by weight: 30-50 parts of hydroxyl resin, 0.1-0.2 parts of leveling agent, 2-4 parts of ultraviolet absorber (Tinuvin 401) , 20-40 parts of solvent, 5-10 parts of small molecular weight polycaprolactone glycol, 0.1-0.5 parts of smooth hand feel agent, 1-3 parts of anti-graffiti agent, 1-3 parts of hydrophobic agent, 0. 01 - 1.5 parts and 15 - 40 parts of curing agent.
  • the hydroxyl resin is hydroxyl acrylic resin (hydroxyl-containing polyurethane resin produced by Guangdong Sanqi New Materials Co., Ltd., model number L - 1360), polyester (polyester produced by Covestro, model number Desmophen 1652, Desmophen 670BA), Polyether (produced by Nanjing Zhongshan Petrochemical Co., Ltd., model number N - 330 polyether), epoxy resin (produced by Allnex, model number EBECRYL 3700) and polycarbonate (produced by Covestro, model number Desmophen C1200) One or a combination of two or more.
  • hydroxyl acrylic resin hydroxyl-containing polyurethane resin produced by Guangdong Sanqi New Materials Co., Ltd., model number L - 1360
  • polyester polyester produced by Covestro, model number Desmophen 1652, Desmophen 670BA
  • Polyether produced by Nanjing Zhongshan Petrochemical Co., Ltd., model number N - 330 polyether
  • the leveling agent is silicone-modified polyetheroxyane (BYK - 333), polyether-modified polydimethylsiloxane (BYK - 306, BYK - 331, BYK - 378), aralkyl-modified One or a combination of two or more methylalkyl polysiloxanes (BYK - 322).
  • the solvent is one or a combination of two or more of ester solvents, amide solvents, and ether solvents, preferably ethyl acetate.
  • the catalyst is one of an organic bismuth catalyst (Borchi Kat 22, Bayer) and an organic tin catalyst (produced by Shule Industrial (Shanghai) Co., Ltd., model 4202 catalyst).
  • the curing agent is one or a combination of two of HDI/IPDI curing agent and HDI trimer curing agent (Desmodur N3390 from Covestro) in any proportion.
  • the function of the small molecular weight polycaprolactone glycol (Hunan Juren Chemical New Material Technology Co., Ltd. PCL - 2044, 2053) is to reduce the hardness of the soft film layer and increase the elongation at break.
  • the hand-smooth agent includes polysiloxane-polyether copolymer, tape Hydroxyl polyether-modified silicone, acrylate functional polyester-modified dimethylsiloxane solution, etc., preferably Evonik’s Tego - 410 and Tego - 450, AFCONA’s 3030, 3031, and 3085 One or several.
  • the anti-graffiti agent is to provide smooth repair coating performance.
  • the anti-graffiti agent is selected from a hydroxyl-containing silicone-modified polyacrylic acid solution, preferably BYK - One or more of SILCLEAN3700, 3710, 3720, Tego 5000, Tego5001.
  • the function of the hydrophobic agent is to provide hydrophobicity.
  • the hydrophobic agent is a fluorine-containing block polymer solution, selected from Sinyue's KY - 108, KY - 1203, KY - 1206, CoatFilmTM UVF - 103, etc. .
  • a method for preparing the thermally cured PU adhesive film as described above, the steps are as follows:
  • the heat-curing PU adhesive film of the present invention can not only be directly coated with silicone, but can also directly achieve anti-fingerprint, slippery, high water drop angle and other functions. It simplifies the original functional coating, has a simpler structure, and is easy to construct at the manufacturing end of the protective film, eliminating the need for The step of applying functional coating simplifies the process and cost of the protective film manufacturing end.
  • This invention aims to replace the traditional cast TPU process by coating heat-cured PU glue on the release film to form a film.
  • the production process is simple and efficient, and the adhesive film is white and transparent; the molecules of the heat-cured PU adhesive film are A cross-linked network is formed, with better mechanical properties, it can be directly coated with silicone, the structure is simpler, and construction is convenient; at the same time, a specially prepared low-viscosity isocyanate curing agent is selected to solve the problem of low construction solid content of existing ordinary thermosetting PU adhesive films. Poor leveling during thick coating can easily lead to problems such as bubble spots, orange peel lines, edge shrinkage and difficulty in film formation.
  • anti-fingerprint, slippery, high water drop angle and other functions can be achieved on the heat-cured PU film. , no need to apply functional coating, simplifying the protective film manufacturing process.
  • Example 1 40 parts of hydroxyl resin, 0.2 parts of silicone-modified polyetheroxyane, 3 parts of ultraviolet absorber, 5 parts of ethyl acetate, 30 parts of butyl acetate, 0.05 parts of organic bismuth catalyst, HDI three 10 parts of polymer curing agent and 10 parts of HDI/IPDI curing agent.
  • glue component A (1) Mix the above-mentioned parts by weight of hydroxyl resin, silicone-modified polyetheroxyane, ultraviolet absorber, ethyl acetate, butyl acetate and organic bismuth catalyst to obtain glue component A, which is ready for use.
  • Example 1 Tear open the side with low release force and apply silica gel. After the silicone gel solidifies, tear open the side with high release force and apply smooth coating to obtain Example 1.
  • Example 2 30 parts of hydroxyl resin, 0.1 part of silicone-modified polyetheroxyane, 0.1 part of polyether-modified polydimethylsiloxane, 2 parts of ultraviolet absorber, 30 parts of ethyl acetate, 5 parts of methyl isobutyl ketone, 0.05 parts of organic bismuth catalyst, 10 parts of HDI trimer curing agent, 10 parts of HDI/IPDI curing agent, 10 parts of small molecular weight polycaprolactone glycol, 2 parts of hydrophobic agent , 0.5 parts of hand smooth agent and 3 parts of anti-graffiti agent.
  • Embodiment 3 50 parts of hydroxyl resin, 0.2 parts of silicone modified polyether oxane, 3 parts of ultraviolet absorber, 5 parts of ethyl acetate, 15 parts of butyl acetate, 0.05 parts of organic bismuth catalyst, HDI three 10 parts of polymer curing agent, 10 parts of HDI/IPDI curing agent, 5 parts of small molecular weight polycaprolactone glycol.
  • Example 4 45 parts of hydroxyl resin, 0.1 part of silicone-modified polyetheroxane, 0.05 part of polyether-modified polydimethylsiloxane, aralkyl-modified methylalkyl polysiloxane 0.05 parts of alkane, 2 parts of UV absorber, 5 parts of methyl isobutyl ketone, 25 parts of butyl acetate, 0.05 parts of organic bismuth catalyst, 10 parts of HDI trimer curing agent, 10 parts of HDI/IPDI curing agent 0.5 parts and 0.5 parts of hand smooth agent.
  • Embodiment 5 40 parts of hydroxyl resin, 0.2 parts of silicone modified polyether oxane, 3 parts of ultraviolet absorber, 10 parts of ethyl acetate, 30 parts of butyl acetate, 0.05 parts of organic bismuth catalyst, HDI/ 20 parts of IPDI curing agent.
  • glue component A (1) Mix the above-mentioned parts by weight of hydroxyl resin, silicone-modified polyetheroxyane, ultraviolet absorber, ethyl acetate, butyl acetate and organic bismuth catalyst to obtain glue component A, which is ready for use.
  • Comparative Example 1 An 8-inch TPU hydrogel film mobile phone film purchased from Dongguan Sachuan Electronic Technology Co., Ltd.
  • Comparative Example 2 TPU ultra-thin soft film model F-Samsung note series TPU purchased from Shenzhen Nas Technology Co., Ltd.
  • the above data show that under the same hardness conditions, the mechanical properties of the PU film of the present invention are equivalent to or even better than cast TPU, and the aging resistance is significantly improved.
  • the adhesive films in the examples can bond to silicone very well.
  • the protective film made of the adhesive film of Example 1 is added with HDI trimer curing agent and HDI/IPDI curing agent to double-cure the PU adhesive film, so that the PU adhesive film has better stiffness and hardness, and the protective film obtained
  • the film has good scratch resistance and is not prone to marks.
  • the adhesive films of Example 2 and Example 4 add a smooth hand feel agent into the formula, which has a repairing and smooth effect. It can be used by directly coating the silicone gel to reduce the process and reduce the cost.
  • the aging resistance of Examples 1-5 can reach more than 2500 hours, which is significantly improved compared to the 1000 hours of aging time of commonly used TPU.
  • silicone-modified polyether A composite leveling agent formed of oxane, polyether-modified polydimethylsiloxane and aralkyl-modified methylalkylpolysiloxane in a ratio of 2:1:1 can further improve the flow of PU glue. Flatness, enhances the toughness of PU film.

Abstract

一种HDI/IPDI固化剂、制备方法、用途及热固化PU胶膜，固化剂由酯类溶剂、TMP、HDI、IPDI和DBTDL制成；制得的固化剂交联结构比HDI更紧密；固化剂比传统的固化剂粘度要低，流平性更好，提高涂布时的施工固含，解决厚涂时流平不佳、易出现气泡点、橘皮纹和边缘收缩等问题，而且还能有效提高热固化PU胶膜的力学性能；通过在离型膜上涂布成膜的方式替代传统流延TPU工艺，生产工艺简单且高效，胶膜水白透明；制得的热固化PU胶膜的分子之间形成了交联网络，力学性能更好、可直涂硅胶，结构更简单，施工方便，解决了传统热塑性的TPU直涂硅胶易被溶剂溶胀发白，且传统TPU中的小分子增塑剂易使硅胶中的铂金催化剂失活，需要贴合中间隔离层的问题，降低了保护膜制造端的工艺难度和成本。

Description

一种HDI/IPDI固化剂、制备方法、用途及热固化PU胶膜 技术领域
本发明涉及一种保护膜基材，特别是一种HDI/IPDI固化剂、制备方法、用途及热固化PU胶膜。
 背景技术
保护膜在功能上讲是贴合在被保护的实体物品表面的一层胶膜，通常的结构为上保膜+功能涂层+保护膜基材+硅胶层+离型膜。目前市场上常用的保护膜基材包括PET(聚对苯二甲酸乙二醇酯)薄膜、TPU(热塑性聚氨酯)薄膜、PVC(聚氯乙烯)薄膜、PE(聚乙烯)薄膜、OPP(聚丙烯)薄膜，以及一些耐高温的高端膜如PI(聚酰亚胺)薄膜、PEN(聚萘二甲酸乙二醇酯)薄膜和PEEK(聚醚醚酮)薄膜等。
其中TPU薄膜是一类加热可以塑化、溶剂可以溶解的聚氨酯，主要利用挤出机，将TPU胶粒在200℃左右的温度下经过混合、熔融塑化、挤出流延、冷却定型而得到胶膜成品。因聚氨酯是由异氰酸酯硬段和多元醇软段组成的兼具有塑性和弹性为一体的嵌段型聚合物，具有硬度和弹性可调控范围广，耐磨性、耐候性和耐化学品性优异，因此被广泛应用于电子、医疗、建筑、建材、航天航空领域。
虽然目前TPU已逐渐取代软质PVC成为更为常用的保护膜基材，但是其流延挤出工艺复杂、高温塑化易使胶膜黄变，影响透明度和雾度不佳，限制了应用场景；并且热塑性的TPU直涂硅胶易被溶剂溶胀发白，且其中的小分子增塑剂易使硅胶中铂金催化剂失活，需要贴合中间隔离层，增加了保护膜制造端的工艺难度和成本。
导致原因：TPU胶膜在流延挤出时需要经过200℃左右的高温塑化，易使胶膜黄变，无法应用于对透明度和雾度要求较高的领域；并且热塑性的TPU分子间没有形成交联网络，直接涂覆硅胶会被其中的溶剂溶胀发白 ，且其中的小分子增塑剂易使硅胶中铂金催化剂失活使硅胶无法固化，一般需要贴合中间隔离层(如PET薄膜)，这增加了保护膜制造端的工序和成本。
热固TPU胶膜是以PU涂层的配方通过优化改良成膜而成，本身流平性不足，现有异氰酸酯固化剂大都粘度较大，容易出现流平不佳，以及泡点、橘皮纹等问题；一般通过降低施工粘度可以改善，但这样无法厚涂，限制了应用范围。
申请号为CN110431173A的专利公开了一种用于制备热塑性聚氨酯膜的方法，其特征在于所述制备方法包括制备包含聚氨酯树脂、第一基于异氰酸酯的固化剂和有机溶剂的聚氨酯树脂组合物；通过将所述聚氨酯树脂组合物施加于基底膜上以及对所述聚氨酯树脂组合物进行热处理来制备包括聚氨酯树脂层的层合体；提供两个层合体以使其接合，使得所述层合体的各自的聚氨酯树脂层彼此相对；以及通过接合的层合体老化来形成包括彼此直接接触的两个聚氨酯树脂层的热塑性聚氨酯膜。该专利设计的热塑性聚氨酯膜的制备方法具有可以容易地制备具有大的厚度和优异的耐久性的热塑性聚氨酯膜的优点。但因该制备方法主要通过两面层合的方法制备聚氨酯膜，具有重涂性差、施工难度大、对聚氨酯树脂层的界面粘合强度范围要求高等缺点。
申请号为CN114149781A的专利公开了TPU复合胶水制备成保护膜的方法。其特征在于，利用脂肪族聚氨酯丙烯酸树脂和酮醛树脂对现有的TPU颗粒进行改性，提高获得的TPU复合胶水固化后形成的TPU胶层的硬度以及模量，可作为涂布软膜层提供指压回弹效果。该专利设计的思路与本发明接近，但因其无法直涂硅胶只相当于改良TPU层力学性能结构，需要多层结构，具有施工步骤繁琐，调整范围窄等缺点。
综上所述，现有技术存在如下缺点：
1、普通热固PU胶膜，施工固含低，厚涂时流平不佳，易出现气泡点、橘皮纹，涂无基材边缘收缩不易成膜等问题。
2、传统TPU胶膜的流延挤出工艺复杂、高温塑化易使胶膜黄变，影响透明度和雾度不佳，限制了应用场景。
3、热塑性的TPU直涂硅胶易被溶剂溶胀发白，或直接使硅胶中铂金催化剂失活使硅胶无法固化，需要贴合中间隔离层，增加了保护膜制造端的工艺难度和成本。
4、普通热固PU胶膜本身不具备抗指纹、滑爽、高水滴角的功能，保护膜制造端需要涂布功能涂层来实现抗指纹、滑爽、高水滴角的功能，增加了保护膜制造端的施工成本，施工工艺复杂。
 技术解决方案
为了克服现有技术的不足，本发明提供一种HDI/IPDI固化剂、制备方法、用途及热固化PU胶膜。
本发明解决其技术问题所采用的技术方案是：
一种HDI/IPDI固化剂，由酯类溶剂、三羟甲基丙烷、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和二月桂酸二丁基锡制成。
所述六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和三羟甲基丙烷之间的摩尔比为(2 .0 -3.0)：(1 .2 -1 .8)：(0.8 -1 .2)。
所述二 月桂酸二丁基锡的重量百分比为0 .03 -0 .08％。
所述酯类溶剂为乙酸丁酯或乙酸乙酯。
一种制备如上所述的HDI/IPDI固化剂的方法，步骤如下：在装有搅拌器、冷凝器、温度计的四口烧瓶中，加入上述酯类溶剂、三羟甲基丙烷(TMP)、六亚甲基二异氰酸酯(HDI)与异佛尔酮二异氰酸酯(IPDI)，边搅拌边加热至80℃，然后保温反应，在保温反应过程中分3 -5次加入二月桂酸二丁基锡(DBTDL)，反应2 .5 -3h直至体系内不溶物质消失，得到HDI/IPDI固化剂。
一种如上所述的HDI/IPDI固化剂的用途，该HDI/IPDI固化剂用于制备保护膜的用途。
一种如上所述的HDI/IPDI固化剂的用途，该HDI/IPDI固化剂用于制备PU胶膜的用途。
一种应用如上所述HDI/IPDI固化剂的热固化PU胶膜，该PU胶膜包括如下重量份数的原料：羟基树脂30 -50份、流平剂0 .1 -0 .2份、紫外线吸收剂2 -4份、溶剂20 -40份、小分子量聚己内酯二元醇5 -10份、手感爽滑剂0 .1 -0 .5份、防涂鸦剂1 -3份、疏水剂1 -3份、催化剂0 .01 -1 .5份和固化剂15 -40份；所述固化剂为HDI/IPDI固化剂或六亚甲基二异氰酸酯三聚体和HDI/IPDI固化剂任意比例的组合物。
所述羟基树脂为羟基丙烯酸树脂、聚酯、聚醚、环氧树脂和聚碳酸酯中的一种或两种以上的组合物；所述流平剂为有机硅改性聚醚氧烷、有机硅改性聚酯多元醇和有机硅改性聚丙烯酸酯中的一种或两种以上的组合物；所述溶剂为酯类溶剂、酰胺类溶剂和醚类溶剂中的一种或两种以上的组合物；所述催化剂为有机铋类催化剂、有机锡类催化剂中的一种。
一种制备如上所述的热固化PU胶膜的方法，步骤如下：
(1)、将上述重量份数的羟基树脂、催化剂、流平剂、紫外线吸收剂、小分子量聚己内酯二元醇、手感爽滑剂、防涂鸦剂、疏水剂和溶剂放入搅拌釜中充分混合，得A组分，待用。
 (2)、将上述重量份数的固化剂加入到搅拌釜中与A组分充分混合，获得PU胶水，待用。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 -4min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。
(4)、收卷后将膜卷置于50℃烘箱房熟化2天，制得带离型膜的热固化PU胶膜。
 有益效果
本发明的有益效果是：
1、本发明通过使用三羟甲基丙烷结合异佛尔酮二异氰酸酯与六亚甲基二异氰酸酯形成HDI/IPDI固化剂，交联结构比六亚甲基二异氰酸酯三聚体更紧密，自制的HDI/IPDI固化剂比传统的异氰酸酯固化剂粘度要低，流平性更好，不仅能提高涂布时的施工固含，解决厚涂时流平不佳、易出现气泡点、橘皮纹和边缘收缩等问题，而且还能有效提高PU胶膜的硬度和韧性。
2、本发明通过HDI/IPDI固化剂制得的PU胶水可在离型膜上直接涂布成膜，替代了传统流延TPU工艺，生产工艺简单且高效，胶膜水白透明。
3、本发明通过HDI/IPDI固化剂制得的热固化PU胶膜的分子之间形成了交联网络，力学性能更好、可直涂硅胶，结构更简单，施工方便，解决了传统热塑性的TPU直涂硅胶易被溶剂溶胀发白或直接使硅胶催化剂失活导致硅胶无法固化的问题，需要贴合中间隔离层的问题，降低了保护膜制造端的工艺难度和成本。
4、本发明的热固化PU胶膜可以通过添加手感爽滑剂、防涂鸦剂和疏水剂，直接在PU胶膜上实现抗指纹、滑爽、高水滴角的功能，简化了原功能涂层，降低了保护膜制造端的施工成本，使施工更加方便。
 本发明的最佳实施方式
在本发明所有实施例中，关于温度和压力没有特别强调的，均为常温常压，关于设备使用没有特别说明的，均按常规设置使用即可。
一种HDI/IPDI固化剂，由乙酸丁酯(化学式：CH 3COO(CH 2) 3CH 3)或乙酸乙酯(化学式 C 4H 8O 2)或NMP(化学式C 5H 9NO)、三羟甲基丙烷(TMP，化学式：CH 3CH 2C(CH 2OH) 3)、六亚甲基二异氰酸酯(HDI，化学式：C 8H 12N 2O 2)、异佛尔酮二异氰酸酯(IPDI，化学式：C 12H 18N 2O 2)和二 月桂酸 二丁基锡(DBTDL，分子式：C 32H 64O 4Sn)制成。
经过探究实验发现，HDI、IPDI与TMP的摩尔比为2 .5:1 .5:1，催化剂DBTDL用量为0 .05％，反应温度为80℃，反应时间3h时可获得低粘度、‑NCO含量最接近理论‑NCO含量的固化剂(通过丙酮‑二正胺滴定法测定固化剂中‑NCO的含量)。
所述HDI/IPDI固化剂的合成方法：在装有搅拌器、冷凝器、温度计的四口烧瓶中，分别加入计量的乙酸丁酯、TMP、HDI与IPDI，以及分多次加入适量催化剂DBTDL，在80℃温度下反应3h，直至体系内不溶物质消失，得到HDI/IPDI固化剂，回收过量的异氰酸酯并入下次投料，测定体系内‑NCO基团的质量分数(理论NCO％为18 .26％，实测约为18 .40％)，并在25℃情况下检测反应产物粘度。
采用IPDI三聚体制备的聚氨酯涂层具有高硬度和高弹性模量的特点，但因其常温下呈现固态，即使经过溶剂稀释后仍然是高粘度难以涂布，施工不方便，本发明通过使用三元醇结合IPDI与HDI形成三聚体，交联结构比单纯用HDI三聚体更紧密，制备高硬度高弹性模量高断裂伸长率并能重复涂布硅胶与爽滑涂层的涂布型软膜。通过采用不同的羟基组分A，硬度可以做到邵氏硬度70A到邵氏硬度70D一系列产品，满足不同设计需要。
一种热固化PU胶膜，该PU胶膜包括如下重量份数的原料：羟基树脂30‑50份、流平剂0 .1 -0 .2份、紫外线吸收剂(Tinuvin 401)2 -4份、溶剂20 -40份、小分子量聚己内酯二元醇5 -10份、手感爽滑剂0 .1 -0.5份、防涂鸦剂1 -3份、疏水剂1 -3份、催化剂0 .01 -1 .5份和固化剂15 -40份。
所述羟基树脂为羟基丙烯酸树脂(广东叁漆新材料有限公司生产、型号为L -1360的含羟基聚氨酯树脂)、聚酯(科思创生产、型号为Desmophen 1652、Desmophen 670BA的聚酯)、聚醚(南京钟山石化有限公司生产、型号为N -330聚醚)、环氧树脂(湛新生产、型号为EBECRYL 3700)和聚碳酸酯(科思创生产、型号为Desmophen C1200)中的一种或两种以上的组合物。
所述流平剂为有机硅改性聚醚氧烷(BYK -333)、聚醚改性聚二甲基硅氧烷(BYK -306、BYK -331、BYK -378)、芳烷基改性甲基烷基聚硅氧烷(BYK -322)中的一种或两种以上的组合物。
所述溶剂为酯类溶剂、酰胺类溶剂、醚类溶剂中的一种或两种以上的组合物，优选乙酸乙酯。
所述催化剂为有机铋类催化剂(Borchi Kat 22 ,拜尔)、有机锡类催化剂(曙乐实业(上海)有限公司生产的、型号为4202催化剂)中的一种。
所述固化剂为HDI/IPDI固化剂和HDI三聚体固化剂(科思创公司Desmodur N3390)中的一种或两种任意比例的组合物。
所述小分子量聚己内酯二元醇(湖南聚仁化工新材料科技有限公司PCL -2044、2053)，其作用是降低软膜层硬度，提高断裂伸长率。
所述手感爽滑剂的作用是节省工艺工序和提高手感爽滑性，考虑到涂层透光率以及光泽度的问题，所述手感爽滑剂包括聚硅氧烷‑聚醚共聚物、带羟基的聚醚改性有机硅、丙烯酸酯官能基的聚酯改性二甲基硅氧烷溶液等类型，优选赢创的Tego -410、Tego -450，AFCONA公司的3030、3031、3085中的一种或几种。
所述防涂鸦剂的作用是提供爽滑修复涂层性能，考虑到表面流平和耐油性笔涂鸦的问题，所述的耐涂鸦剂选自含羟基的有机硅改性聚丙烯酸溶液，优选BYK -SILCLEAN3700、3710、3720、Tego 5000、Tego5001中的一种或几种。
所述疏水剂的作用是提供疏水性，所述的疏水剂为含氟嵌段聚合物溶液，选自信越的KY -108、KY -1203、KY -1206，柯紐新材CoatFilmTM UVF -103等。
一种制备如上所述的热固化PU胶膜的方法，步骤如下：
(1)、将上述重量份数的羟基树脂、催化剂、流平剂、紫外线吸收剂、小分子量聚己内酯二元醇、手感爽滑剂、防涂鸦剂、疏水剂和溶剂放入搅拌釜中充分混合，得A组分，待用。
(2)、将上述重量份数的固化剂加入到搅拌釜中与A组分充分混合，获得PU胶水，待用。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 -4min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。热固化PU胶膜采用涂布工艺，简单且高效。
(4)、收卷后将膜卷置于50℃烘箱房熟化2天，制得带离型膜的PU胶膜。
使用时撕开低离型力的一面涂布硅胶。
本发明的热固化PU胶膜不仅可以直涂硅胶，还可以直接实现抗指纹、滑爽、高水滴角等功能，简化了原功能涂层，结构更简单，保护膜制造端施工方便，无需再涂布功能涂层的步骤，简化了保护膜制造端的工序和成本。
本发明旨在通过在离型膜上涂布热固化PU胶水而成膜的方式替代传统流延TPU工艺，生产工艺简单且高效，胶膜水白透明；该热固化PU胶膜的分子之间形成了交联网络，力学性能更好、可直涂硅胶，结构更简单，施工方便；同时选用特殊制备的低粘度异氰酸酯固化剂，解决了现有普通热固PU胶膜，施工固含低，厚涂时流平不佳，易出现气泡点、橘皮纹、边缘收缩难以成膜等问题；此外还通过配方设计，在热固化PU胶膜上实现抗指纹、滑爽、高水滴角等功能，无需再涂覆功能涂层，简化了保护膜制造工艺。
本发明的实施方式
为使本发明的目的、技术方案和优点更加清楚明了，下面结合具体实施方式，对本发明进一步详细说明。需要说明的是，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。
实施例1：羟基树脂40份、有机硅改性聚醚氧烷0 .2份、紫外线吸收剂3份、乙酸乙酯5份、乙酸丁酯30份、有机铋催化剂0 .05份、HDI三聚体固化剂10份和HDI/IPDI固化剂10份。
实施例1的制备方法：
(1)、将上述重量份的羟基树脂、有机硅改性聚醚氧烷、紫外线吸收剂、乙酸乙酯、乙酸丁酯和有机铋催化剂混合，获得胶水A组分，待用。
(2)、将100重量份的A组分与10重量份的HDI三聚体固化剂、10重量份的HDI/IPDI固化剂充分混合，获得PU胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 .5min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天，制得带离型膜的PU胶膜。
撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开高离型力的一面涂布爽滑涂层，得实施例1。
实施例2：羟基树脂30份、有机硅改性聚醚氧烷0 .1份、聚醚改性聚二甲基硅氧烷0 .1份、紫外线吸收剂2份、乙酸乙酯30份、甲基异丁基酮5份、有机铋催化剂0 .05份、HDI三聚体固化剂10份、HDI/IPDI固化剂10份、小分子量聚己内酯二元醇10份、疏水剂2份、手感爽滑剂0 .5份和防涂鸦剂3份。
实施例2的制备方法：
(1)、将上述重量份的羟基树脂、有机硅改性聚醚氧烷、聚醚改性聚二甲基硅氧烷、紫外线吸收剂、乙酸乙酯、甲基异丁基酮、有机铋催化剂、小分子量聚己内酯二元醇、疏水剂、手感爽滑剂和防涂鸦剂混合，获得胶水A组分，待用。
(2)、将100重量份的A组分与10重量份的HDI三聚体固化剂、10重量份的HDI/IPDI固化剂充分混合，获得PU胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 .5min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天，制得带离型膜的PU胶膜。
撕开低离型力的一面涂布硅胶，得实施例2。
实施例3：羟基树脂50份、有机硅改性聚醚氧烷0 .2份、紫外线吸收剂3份、乙酸乙酯5份、乙酸丁酯15份、有机铋催化剂0 .05份、HDI三聚体固化剂10份、HDI/IPDI固化剂10份、小分子量聚己内酯二元醇5份。
实施例3的制备方法：
(1)、将上述重量份的羟基树脂、有机硅改性聚醚氧烷、紫外线吸收剂、乙酸乙酯、乙酸丁酯、有机铋催化剂和小分子量聚己内酯二元醇混合，获得胶水A组分，待用。
(2)、将100重量份的A组分与10重量份的HDI三聚体固化剂、10重量份的HDI/IPDI固化剂充分混合，获得PU胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 .5min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天，制得带离型膜的PU胶膜。
 撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开高离型力的一面涂布爽滑涂层，得实施例3。
实施例4：羟基树脂45份、有机硅改性聚醚氧烷0 .1份、聚醚改性聚二甲基硅氧烷0 .05份、芳烷基改性甲基烷基聚硅氧烷0 .05份、紫外线吸收剂2份、甲基异丁基酮5份、乙酸丁酯25份、有机铋催化剂0 .05份、HDI三聚体固化剂10份、HDI/IPDI固化剂10份和手感爽滑剂0 .5份。
实施例4的制备方法：
(1)、将上述重量份的羟基树脂、有机硅改性聚醚氧烷、聚醚改性聚二甲基硅氧烷、芳烷基改性甲基烷基聚硅氧烷、紫外线吸收剂、甲基异丁基酮、乙酸丁酯、有机铋催化剂和手感爽滑剂混合，获得胶水A组分，待用。
(2)、将100重量份的A组分与10重量份的HDI三聚体固化剂、10重量份的HDI/IPDI固化剂充分混合，获得PU胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 .5min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天，制得带离型膜的PU胶膜。
撕开低离型力的一面涂布硅胶，得实施例4。
实施例5：羟基树脂40份、有机硅改性聚醚氧烷0 .2份、紫外线吸收剂3份、乙酸乙酯10份、乙酸丁酯30份、有机铋催化剂0 .05份、HDI/IPDI固化剂20份。
实施例5的制备方法：
(1)、将上述重量份的羟基树脂、有机硅改性聚醚氧烷、紫外线吸收剂、乙酸乙酯、乙酸丁酯和有机铋催化剂混合，获得胶水A组分，待用。
(2)、将100重量份的A组分与20重量份的HDI/IPDI固化剂充分混合，获得PU胶水。
(3)、在50μm的高离型力离型膜上涂布PU胶水，在120℃烘烤3 .5min使胶水表干，形成60 -100μm厚的软膜层，用50μm低离型力的离型膜覆膜收卷。
(4)、收卷后将膜置于50℃烘箱房熟化2天，制得带离型膜的PU胶膜。
撕开低离型力的一面涂布硅胶，待硅胶固化后再撕开高离型力的一面涂布爽滑涂层，得实施例5。
对比例1：购自东莞市佐川电子科技有限公司在售的8寸TPU水凝膜手机贴膜。
对比例2：购自深圳市纳斯科技有限公司在售的型号为F‑三星note系列TPU的TPU超薄软膜。
申请人对所得的实施例1 -5和对比例1 -2的硬度、断裂伸长率、拉伸强度、弹性模量、耐老化性和指压回弹性做了测试。
(1)PU胶膜硬度测试具体方法：采用GB/T 531 .1 -2008，采用的是压针式的数显邵氏硬度计A型和D型，测试PU胶膜胶水60℃48h后形成的硬度块，在试样表面不同位置进行5次测试测量取中值。
(2)PU胶膜断裂伸长率、拉伸强度测试具体方法：采用GB/T6344 -2008，采用的是拉力试验机，将PU胶膜离型膜撕除，用刀模冲切成哑铃状，将拉力试验机载荷值置于零位，把胶膜样夹在拉力试验机夹具上，仔细而对称地调整试样，使拉力均匀分布在试样横截面上，对试样施加0 .5％预伸长。完成预伸长后将伸长测量系统伸长示值清零然后启动拉力试验机，拉伸速度未5mm/min，记录拉伸过程最大载荷和试样断裂瞬间两夹具伸长率示数，并继续试验直至获得5个结果。取平均值。
(3)PU胶膜弹性模量测试具体方法：将PU胶膜离型膜撕除，裁剪成50mm(MD向)×20mm(TD向)的矩形长条，用拉力机夹具夹持试样，要使试样MD向与上、下夹具的中心连线重合，并且要松紧适宜，以防止试样滑脱或断在夹具内，设定试验速度为5mm/min，拉伸应变为5％，进行试验，记录TPU胶层的模量数据。
(4)PU胶膜老化试验测试具体方法：采用GB/T 23987 -2009，将PU胶膜裁剪成合适的大小，置入老化机，使用以下循环：在辐照度为0 .68W/cm2、黑板温度70℃的UVA条件下辐照8h，然后在黑板温度50℃的条件下凝露4h，然后再回到辐照阶段，如此循环，观察PU胶膜外观。
(5)PU胶膜指压回弹测试具体方法：采用硅胶为粘附层的复合结构保护膜时，将复合结构保护膜贴合在TP玻璃(AF屏幕，水滴角＞110±5°)上，撕除上保后，将三菱HB铅笔笔芯削成5mm的圆柱形并在400目砂纸上磨平，装在铅笔硬度测试仪上，施加在笔尖上的载荷为350g，铅笔与待测表面的夹角为45°，在待测位置匀速推动铅笔向前滑动约5mm长，不同位置划5笔。观察复合结构保护膜表面是否有划痕，有划痕多长时间内可以恢复。
测试结果如下表所示：
由以上数据表明，在同样的硬度情况下，本发明的PU胶膜力学性能与流延的TPU相当甚至更好，同时耐老化有明显提升。相比于一般TPU难以粘接硅胶，实施例中的胶膜均能很好的粘接硅胶。实施例1胶膜制成的保护膜，由于加入了HDI三聚体固化剂和HDI/IPDI固化剂来双重固化PU胶膜，使PU胶膜具有较好的挺度和硬度，制得的保护膜具有良好的耐划伤性和不易有痕迹。实施例2和实施例4胶膜在配方中加入了手感爽滑剂，本身具有修复爽滑效果直接涂布硅胶便可使用减少工序降低成本。实施例1‑5耐老化均能达到2500h以上，相比常用TPU老化时间1000小时有明显提升。
申请人还进一步研究了流平剂的种类和配比对PU胶水的流平性的影响，但还未形成详细的、完整的实验数据，根据现有的实验数据表明，有机硅改性聚醚氧烷、聚醚改性聚二甲基硅氧烷和芳烷基改性甲基烷基聚硅氧烷以2:1:1的配比形成的复合流平剂可以进一步改善PU胶水的流平性，增强PU胶膜的韧性。
以上的实施方式不能限定本发明创造的保护范围，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。

Claims (10)

  1. 一种HDI/IPDI固化剂，其特征在于由酯类溶剂、三羟甲基丙烷、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和二月桂酸二丁基锡制成。
  2. 根据权利要求1所述的HDI/IPDI固化剂，其特征在于所述六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯和三羟甲基丙烷之间的摩尔比为(2.0 -3.0)：(1 .2 -1 .8)：(0.8 -1 .2)。
  3. 根据权利要求2所述的HDI/IPDI固化剂，其特征在于所述二月桂酸二丁基锡的重量百分比为0 .03 -0 .08％。
  4. 根据权利要求1所述的HDI/IPDI固化剂，其特征在于所述酯类溶剂为乙酸丁酯或乙酸乙酯。
  5. 一种制备如权利要求1-4任一所述的HDI/IPDI固化剂的方法，其特征在于步骤如下：在装有搅拌器、冷凝器、温度计的四口烧瓶中，加入上述酯类溶剂、三羟甲基丙烷、六亚甲基二异氰酸酯与异佛尔酮二异氰酸酯，边搅拌边加热至70 -90℃，然后保温反应，在保温反应过程中分3 -5次加入二月桂酸二丁基锡，反应2 .5 -3h直至体系内不溶物质消失，得到HDI/IPDI固化剂。
  6. 一种如权利要求1-4任一所述的HDI/IPDI固化剂HDI/IPDI的用途，其特征在于该HDI/IPDI固化剂用于制备保护膜的用途。
  7. 一种如权利要求1-4任一所述的HDI/IPDI固化剂的用途，其特征在于该HDI/IPDI固化剂用于制备PU胶膜的用途。
  8. 一种应用如权利要求1-4任一所述HDI/IPDI固化剂的热固化PU胶膜，其特征在于该PU胶膜包括如下重量份数的原料：羟基树脂30 ‑50份、流平剂0 .1 -0 .2份、紫外线吸收剂2 -4份、溶剂20 -40份、小分子量聚己内酯二元醇5 -10份、手感爽滑剂0 .1 -0.5份、防涂鸦剂1 -3份、疏水剂1 -3份、催化剂0 .01 -1 .5份和固化剂15 -40份；所述固化剂为HDI/IPDI固化剂或六亚甲基二异氰酸酯三聚体和HDI/IPDI固化剂任意比例的组合物。
  9. 根据权利要求8所述的热固化PU胶膜，其特征在于所述羟基树脂为羟基丙烯酸树脂、聚酯、聚醚、环氧树脂和聚碳酸酯中的一种或两种以上的组合物；所述流平剂为有机硅改性聚醚氧烷、聚醚改性聚二甲基硅氧烷和芳烷基改性甲基烷基聚硅氧烷中的一种或两种以上的组合物；所述溶剂为酯类溶剂、酰胺类溶剂和醚类溶剂中的一种或两种以上的组合物；所述催化剂为有机铋类催化剂、有机锡类催化剂中的一种。
  10. 一种制备如权利要求8所述的热固化PU胶膜的方法，其特征在于步骤如下：
     (1)、将上述重量份数的羟基树脂、催化剂、流平剂、紫外线吸收剂、小分子量聚己内酯二元醇、手感爽滑剂、防涂鸦剂、疏水剂和溶剂放入搅拌釜中充分混合，得A组分，待用；
     (2)、将上述重量份数的固化剂加入到搅拌釜中与A组分充分混合，获得PU胶水，待用；
     (3)、在30 -70μm的高离型力离型膜上涂布PU胶水，在110 -130℃烘烤3 -4min使胶水表干，形成60 -100μm厚的软膜层，用30 -70μm低离型力的离型膜覆膜收卷；
    (4)、收卷后将膜卷置于40 -60℃烘箱房熟化1 -3天，制得带离型膜的热固化PU胶膜。
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CN109824863A (zh) * 2019-02-22 2019-05-31 上海稻畑精细化工有限公司 一种聚氨酯固化剂的制备方法
CN115181245A (zh) * 2022-08-16 2022-10-14 广东鼎立森新材料有限公司 一种hdi/ipdi固化剂、制备方法、用途及热固化pu胶膜

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