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CN103594628B - A kind of organic thin film solar cell and preparation method thereof - Google Patents

A kind of organic thin film solar cell and preparation method thereof Download PDF

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CN103594628B
CN103594628B CN201310589687.2A CN201310589687A CN103594628B CN 103594628 B CN103594628 B CN 103594628B CN 201310589687 A CN201310589687 A CN 201310589687A CN 103594628 B CN103594628 B CN 103594628B
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sensitive glue
buffer layer
cationic
photoactive layer
salt
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CN103594628A (en
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于军胜
王煦
李�杰
王瀚雨
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University of Electronic Science and Technology of China
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a kind of organic thin film solar cell and preparation method thereof, this solar battery structure is followed successively by substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer and metallic cathode from top to bottom, and in described photoactive layer, being mixed with mass ratio is the ultraviolet sensitivity glue of 0.03-6%; Described ultraviolet sensitivity glue is the mixed system of free radical type ultraviolet sensitivity glue and cationic ultraviolet sensitivity glue. The invention solves the poor problem of tack between the anode buffer layer of organic thin film solar cell and photoactive layer, increase the interphase match between anode buffer layer and photoactive layer, improved the high-low temperature resistant characteristic of device simultaneously, particularly heat-resisting ability, has improved the working life of device.

Description

一种有机薄膜太阳能电池及其制备方法A kind of organic thin film solar cell and preparation method thereof

技术领域technical field

本发明属于有机聚合物光伏器件或有机半导体薄膜太阳能电池领域,具体涉及一种有机薄膜太阳能电池及其制备方法。The invention belongs to the field of organic polymer photovoltaic devices or organic semiconductor thin-film solar cells, and in particular relates to an organic thin-film solar cell and a preparation method thereof.

背景技术Background technique

能源紧缺和环境恶化等问题已经成为人类生存和发展所面临的重要问题。人类过度开发有限的不可再生能源,使人类目前所依赖的传统能源如煤炭、石油和天然气等出现资源枯竭,并由此产生的全球能源争夺战日益进入白热化阶段。众所周知,清洁能源的种类有风能、水能、地热能和太阳能等,但前三者受限于地域或开发成本,目前并未大面积推广使用。而太阳能占有地球总能量的99%以上,并且没有污染,成为科学家开发和利用的新能源之一。虽然硅单晶太阳能电池能量转换效率很高并且技术较为成熟,但其加工工艺非常复杂,材料要求苛刻且不易进行大面积柔性加工,以及某些材料具有毒性使制备成本居高不下。有机薄膜太阳能电池以其材料合成容易,原料来源广泛、制作工艺简单且成本低廉、耗能少、可制作柔性器件以及易于大规模生产等优势,获得了科学家的高度重视和浓厚兴趣。Issues such as energy shortage and environmental degradation have become important issues facing human survival and development. The over-exploitation of limited non-renewable energy resources by human beings has exhausted the resources of traditional energy sources such as coal, oil and natural gas on which human beings currently rely, and the resulting global energy competition has increasingly entered a white-hot stage. As we all know, the types of clean energy include wind energy, water energy, geothermal energy and solar energy, etc., but the first three are limited by geographical area or development cost, and have not been widely used at present. Solar energy accounts for more than 99% of the total energy of the earth, and has no pollution. It has become one of the new energy sources developed and utilized by scientists. Although the energy conversion efficiency of silicon monocrystalline solar cells is very high and the technology is relatively mature, its processing technology is very complicated, the material requirements are harsh and it is difficult to perform large-area flexible processing, and some materials are toxic, which makes the preparation cost high. Organic thin-film solar cells have attracted great attention and interest from scientists due to their advantages such as easy synthesis of materials, wide sources of raw materials, simple and low-cost manufacturing processes, low energy consumption, flexible devices and easy mass production.

通过近年来的发展,有机薄膜太阳能电池的能量转换效率有了突飞猛进的提高,不断接近15%的实用化的水平。然而有机薄膜太阳能电池的使用寿命偏低,一直是阻碍其市场化发展的瓶颈。由于现实使用环境的复杂,有机薄膜太阳能器件需要有很好的耐高低温特性和耐水氧特性,甚至对于柔性器件来说的弯曲、弯折特性。阳极缓冲层与光活性层的界面失配,是器件稳定性差的众多原因之一。由于通常采用的PEDOT:PSS阳极缓冲层是亲水性的,而光活性层通常是疏水性的,导致了阳极缓冲层与光活性层结合力差,受热或受冷使界面应力发生变化时极易发生脱离、剥落的现象,使器件性能迅速衰减。如何解决阳极缓冲层与光活性层界面的附着力问题,对增加有机薄膜太阳能电池的工作稳定性、提高器件的寿命起着十分重要的作用。Through the development in recent years, the energy conversion efficiency of organic thin film solar cells has been improved by leaps and bounds, approaching the practical level of 15%. However, the low service life of organic thin film solar cells has always been a bottleneck hindering its market development. Due to the complexity of the actual use environment, organic thin film solar devices need to have good high and low temperature resistance and water and oxygen resistance, and even bending and bending characteristics for flexible devices. The interface mismatch between the anode buffer layer and the photoactive layer is one of the many reasons for poor device stability. Since the commonly used PEDOT:PSS anode buffer layer is hydrophilic, while the photoactive layer is usually hydrophobic, resulting in poor bonding between the anode buffer layer and the photoactive layer, and the interface stress is extremely sensitive when heated or cooled. It is prone to detachment and peeling, which makes the device performance rapidly decay. How to solve the problem of adhesion between the anode buffer layer and the photoactive layer interface plays a very important role in increasing the working stability of organic thin film solar cells and improving the life of the device.

发明内容Contents of the invention

本发明所要解决的问题是如何提供一种有机薄膜太阳能电池及其制备方法,目的是解决有机薄膜太阳能电池的阳极缓冲层与光活性层之间附着性差的问题,增加阳极缓冲层与光活性层之间的界面匹配性,同时改善有机薄膜太阳能电池的耐高低温特性,特别是耐高温能力,提高有机薄膜太阳能电池的工作寿命。The problem to be solved by the present invention is how to provide an organic thin film solar cell and its preparation method, the purpose is to solve the problem of poor adhesion between the anode buffer layer and the photoactive layer of the organic thin film solar cell, and increase The interface matching between them can improve the high and low temperature resistance characteristics of organic thin film solar cells, especially the high temperature resistance, and improve the working life of organic thin film solar cells.

为了实现上述目的,本发明采用的技术方案是:In order to achieve the above object, the technical scheme adopted in the present invention is:

一种有机薄膜太阳能电池,其特征在于,该太阳能电池结构从下到上依次为衬底、透明导电阳极ITO、阳极缓冲层、光活性层、阴极缓冲层和金属阴极,所述光活性层中掺有质量比为0.03-6%的紫外敏感胶;所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。An organic thin film solar cell is characterized in that, the solar cell structure is successively substrate, transparent conductive anode ITO, anode buffer layer, photoactive layer, cathode buffer layer and metal cathode from bottom to top, and in the photoactive layer It is mixed with ultraviolet sensitive glue with a mass ratio of 0.03-6%. The ultraviolet sensitive glue is a mixed system of free radical ultraviolet sensitive glue and cationic ultraviolet sensitive glue.

进一步地,所述自由基型紫外敏感胶原料包括97-99.5%的基础树脂、0.2-1%的单体、0.1-1%的光引发剂和0.2-2%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括97-99.5%的阳离子单体、0.4-2%的稀释剂和0.1-2%的阳离子光引发剂。Further, the free radical type UV-sensitive rubber raw material includes 97-99.5% of base resin, 0.2-1% of monomer, 0.1-1% of photoinitiator and 0.2-2% of photosensitizer and auxiliary agent; The above-mentioned cationic UV-sensitive rubber raw material includes 97-99.5% cationic monomer, 0.4-2% diluent and 0.1-2% cationic photoinitiator.

进一步地,所述基础树脂包括不饱和聚酯树脂、丙烯酸系树脂和多硫醇-多烯体系;所述单体包括苯乙烯及其衍生物、单官能团或多官能团丙烯酸酯;所述光引发剂包括安息香及其衍生物安息香甲醚、安息香乙醚、安息香异丙醚和乙酰苯衍生物;光敏剂包括二苯甲酮、硫杂蒽醌和米蚩酮;助剂包括增塑剂、触变剂、填充剂、防静电剂、阻燃剂和偶联剂;所述阳离子单体包括环氧树脂或改性环氧树脂或含氟以及不含氟的混合树脂或者脂肪族和双酚D-型混合环氧树脂;所述稀释剂包括活性环氧树脂稀释剂以及环醚、环内酯、乙烯基醚单体作为光固化树脂的稀释剂;所述阳离子光引发剂有二芳基碘鎓盐、三芳基碘鎓盐、三芳基硫鎓盐、三芳基硒鎓盐。Further, the base resin includes unsaturated polyester resin, acrylic resin and polythiol-polyene system; the monomer includes styrene and its derivatives, monofunctional or multifunctional acrylate; the photoinitiated Agents include benzoin and its derivatives benzoin methyl ether, benzoin ether, benzoin isopropyl ether and acetophenone derivatives; photosensitizers include benzophenone, thioxanthraquinone and Michler ketone; additives include plasticizers, thixotropic agent, filler, antistatic agent, flame retardant and coupling agent; the cationic monomer includes epoxy resin or modified epoxy resin or fluorine-containing and fluorine-free mixed resin or aliphatic and bisphenol D- Type mixed epoxy resin; the diluent includes active epoxy resin diluent and cyclic ether, cyclic lactone, vinyl ether monomer as the diluent of photocurable resin; the cationic photoinitiator has diaryliodonium salt, triaryl iodonium salt, triaryl sulfonium salt, triaryl selenium salt.

进一步地,所述丙烯酸系树脂包括聚酯-丙烯酸酯、环氧-丙烯酸酯、氨基甲酸酯-丙烯酸酯和聚醚-丙烯酸酯。Further, the acrylic resin includes polyester-acrylate, epoxy-acrylate, urethane-acrylate and polyether-acrylate.

进一步地,所述多硫醇-多烯体系为下列结构式的物质:Further, the polythiol-polyene system is a substance of the following structural formula:

进一步地,所述混合体系原料包括环氧树脂E-51,二芳基碘鎓盐和二异丙基噻唑酮。Further, the mixed system raw materials include epoxy resin E-51, diaryliodonium salt and diisopropylthiazolone.

进一步地,所述混合体系原料包括双酚A环氧树脂,硫鎓离子六氟磷酸盐和硫鎓离子六氟锑酸盐,丁基缩水甘油醚,长碳链缩水甘油醚,羟基单体,二官能和三官能的聚己内酯多元醇。Further, the mixed system raw materials include bisphenol A epoxy resin, sulfonium ion hexafluorophosphate and sulfonium ion hexafluoroantimonate, butyl glycidyl ether, long carbon chain glycidyl ether, hydroxyl monomer, Difunctional and trifunctional polycaprolactone polyols.

进一步地,所述混合体系原料包括三缩四乙二醇二甲基丙烯酸酯,3,4-环氧环己基甲基-3’,4’-环氧环己烷羧酸酯,α-羟基环己基苯酮,2,2-二甲氧基-2-苯基苯乙酮,安息香二甲醚,六氟磷酸二苯基碘鎓盐。Further, the mixed system raw materials include tetraethylene glycol dimethacrylate, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, α-hydroxy Cyclohexylbenzophenone, 2,2-dimethoxy-2-phenylacetophenone, benzoin dimethyl ether, diphenyliodonium hexafluorophosphate.

进一步地,所述混合体系原料包括2-乙二醇烯丙基醚,环氧丙烯酸树脂,二甲苯基碘鎓盐,2,2-二甲氧基-2-苯基苯乙酮,2-羟基-2-甲基苯丙酮。Further, the mixed system raw materials include 2-ethylene glycol allyl ether, epoxy acrylic resin, xylyl iodonium salt, 2,2-dimethoxy-2-phenylacetophenone, 2- Hydroxy-2-methylpropiophenone.

一种有机薄膜太阳能电池的制备方法,其特征在于,包括以下步骤:A method for preparing an organic thin film solar cell, comprising the following steps:

①先对预先制备好透明导电阳极ITO的衬底进行清洗,清洗后干燥;① Clean the pre-prepared transparent conductive anode ITO substrate, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆、印刷或喷涂阳极缓冲层,并将所形成的薄膜进行退火处理;② Spin-coat, print or spray-coat the anode buffer layer on the surface of the transparent conductive anode ITO, and anneal the formed film;

③在阳极缓冲层表面旋转涂覆、印刷或喷涂掺有质量比为0.03-6%的紫外敏感胶的光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系;③ On the surface of the anode buffer layer, spin coating, printing or spraying a photoactive layer mixed with a mass ratio of 0.03-6% UV-sensitive glue, and annealing the formed film, the UV-sensitive glue is free radical type Mixed system of UV-sensitive glue and cationic UV-sensitive glue;

④对步骤③得到的光活性层进行紫外光处理;④ carrying out ultraviolet light treatment to the photoactive layer obtained in step ③;

⑤在光活性层表面蒸镀、旋转涂覆或喷涂阴极缓冲层;⑤Evaporation, spin coating or spray coating of the cathode buffer layer on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极。⑥Vapor-deposit a metal cathode on the surface of the cathode buffer layer.

与现有技术相比,本发明的有益效果在于:(1)经过紫外光处理加入紫外敏感胶的光活性层,部分不饱和键在阳极缓冲层与光活性层界面处交联,增加了这两层的之间附着力,使该界面在高低温环境中更加稳定,从而提高器件的耐高低温能力;(2)经紫外光处理后的掺有适量紫外敏感胶的光活性层,不饱和键之间的交联使光活性层更加致密,阻隔了水氧对光电转换过程的影响,提高有机薄膜太阳能电池的空气稳定性;(3)适量的紫外敏感胶的加入,不会对光活性层的吸收产生影响。Compared with the prior art, the beneficial effect of the present invention lies in: (1) after ultraviolet light treatment, the photoactive layer added with UV-sensitive glue, some unsaturated bonds are cross-linked at the interface between the anode buffer layer and the photoactive layer, which increases the The adhesion between the two layers makes the interface more stable in high and low temperature environments, thereby improving the high and low temperature resistance of the device; (2) The photoactive layer mixed with an appropriate amount of UV-sensitive glue after UV treatment is unsaturated The cross-linking between the bonds makes the photoactive layer denser, blocks the influence of water and oxygen on the photoelectric conversion process, and improves the air stability of the organic thin film solar cell; (3) The addition of an appropriate amount of UV-sensitive adhesive will not affect the photoactive layer absorption.

附图说明Description of drawings

图1是本发明所提供的有机薄膜太阳能电池结构示意图;Fig. 1 is the structural representation of the organic thin film solar cell provided by the present invention;

图2是未采用紫外敏感胶的有机薄膜太阳能电池和本发明实施例1(采用紫外敏感胶)的有机薄膜太阳能电池在不同环境温度下工作的归一化效率随温度变化曲线图;Fig. 2 is a graph showing the normalized efficiency of the organic thin-film solar cell without UV-sensitive glue and the organic thin-film solar cell of Example 1 of the present invention (using UV-sensitive glue) working at different ambient temperatures as a function of temperature;

图中标记:1、衬底,2、透明导电阳极ITO,3、阳极缓冲层,4、光活性层,5、阴极缓冲层,6、金属阴极。Marks in the figure: 1. substrate, 2. transparent conductive anode ITO, 3. anode buffer layer, 4. photoactive layer, 5. cathode buffer layer, 6. metal cathode.

具体实施方式detailed description

下面将结合附图及具体实施例对本发明作进一步的描述,所描述的实施例仅仅是本发明一部分实施例,并不是全部的实施例。基于本发明中的实施例,本领域的普通技术人员在没有做出创造性劳动前提下所获得的其他所用实施例,都属于本发明的保护范围。The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, and the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other used embodiments obtained by persons of ordinary skill in the art without creative efforts all belong to the protection scope of the present invention.

结合图1,本发明提供的有机薄膜太阳能电池,包括从下至上依次设置的衬底1、透明导电阳极ITO2、阳极缓冲层3、光活性层4、阴极缓冲层5和金属阴极6,光活性层4中掺有质量比为0.03-6%的紫外敏感胶;所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。1, the organic thin film solar cell provided by the present invention includes a substrate 1, a transparent conductive anode ITO2, an anode buffer layer 3, a photoactive layer 4, a cathode buffer layer 5 and a metal cathode 6 arranged in sequence from bottom to top, and the photoactive Layer 4 is doped with UV-sensitive glue with a mass ratio of 0.03-6%. The UV-sensitive glue is a mixed system of free radical UV-sensitive glue and cationic UV-sensitive glue.

衬底1是电极和有机薄膜层的依托,它在可见光区域有着良好的透光性能,有一定的防水汽和氧气渗透的能力,有较好的表面平整性。衬底1可以为刚性衬底或柔性衬底;刚性衬底可以是玻璃或蓝宝石,柔性衬底可以是金属箔或聚合物薄膜,聚合物薄膜可以为聚乙烯、聚对苯二甲酸乙二醇酯、聚甲基丙烯酸甲酯、聚碳酸酯、聚氨基甲酸酯、聚酰亚胺、氯醋树脂或聚丙烯酸薄膜。The substrate 1 is the support of the electrodes and the organic thin film layer, and it has good light transmission performance in the visible light region, has a certain ability to prevent moisture and oxygen penetration, and has good surface smoothness. The substrate 1 can be a rigid substrate or a flexible substrate; the rigid substrate can be glass or sapphire, the flexible substrate can be metal foil or a polymer film, and the polymer film can be polyethylene, polyethylene terephthalate ester, polymethylmethacrylate, polycarbonate, polyurethane, polyimide, vinyl or polyacrylic film.

阳极缓冲层3为聚(3,4-亚乙二氧噻吩)与聚苯乙烯基苯磺酸的混合物(本领域的技术人员简称为PEDOT:PSS)或者是氧化钼(MoOx);阳极缓冲层的厚度为10-80nm。The anode buffer layer 3 is a mixture of poly(3,4-ethylenedioxythiophene) and polystyrene benzene sulfonic acid (referred to as PEDOT:PSS for those skilled in the art) or molybdenum oxide (MoO x ); The thickness of the layer is 10-80 nm.

阴极缓冲层5材料为TPBi、BCP、Bphen、LiF中的一种,阳极缓冲层的厚度为1-10nm。The material of the cathode buffer layer 5 is one of TPBi, BCP, Bphen and LiF, and the thickness of the anode buffer layer is 1-10 nm.

金属阴极6材料为Ag、Al、Cu中的一种,金属阴极层的厚度为100-300nm。The material of the metal cathode 6 is one of Ag, Al and Cu, and the thickness of the metal cathode layer is 100-300nm.

光活性层4由电子给体材料(PCDTBT)与电子受体材料(PCBM)混合制备而成,PCDTBT:PCBM混合溶液质量比为1:20-5:1,溶液浓度为1-30mg/ml;光活性层的厚度为40-250nm。The photoactive layer 4 is prepared by mixing electron donor material (PCDTBT) and electron acceptor material (PCBM). The mass ratio of PCDTBT:PCBM mixed solution is 1:20-5:1, and the solution concentration is 1-30mg/ml; The thickness of the photoactive layer is 40-250 nm.

自由基型紫外敏感胶原料包括97-99.5%的基础树脂、0.2-1%的单体、0.1-1%的光引发剂和0.2-2%的光敏剂以及助剂;阳离子型紫外敏感胶原料包括97-99.5%的阳离子单体、0.4-2%的稀释剂和0.1-2%的阳离子光引发剂。Free radical UV-sensitive adhesive raw materials include 97-99.5% base resin, 0.2-1% monomer, 0.1-1% photoinitiator, 0.2-2% photosensitizer and additives; cationic UV-sensitive adhesive raw material Including 97-99.5% cationic monomer, 0.4-2% diluent and 0.1-2% cationic photoinitiator.

基础树脂包括不饱和聚酯树脂、丙烯酸系树脂和多硫醇-多烯体系;所述单体包括苯乙烯及其衍生物、单官能团或多官能团丙烯酸酯。The base resins include unsaturated polyester resins, acrylic resins and polythiol-polyene systems; the monomers include styrene and its derivatives, monofunctional or multifunctional acrylates.

不饱和聚酯树脂:不饱和聚酯是由不饱和的二元酸(或酸酐)混以部分饱和二元酸(或酸酐)与二元醇在引发剂的作用下起反应制成的线型聚酯。在其分子结构中有不饱和的乙烯基单体存在,如果用活泼的乙烯基单体与这类不饱和的乙烯基单体共聚,则交联固化而成为体型结构。一般来说,由这种树脂制得的胶粘剂由于固化过程中体积收缩较大,胶接接头的内应力很大。在胶层的内部容易出现微裂纹而导致胶接力变小;同时,由于高分子链中含有酯键,遇酸、碱容易水解,因而耐介质性和耐水性较差,在高温多湿的环境下容易变形;另外,其固化速度较慢,因此,表现出较差的综合性能,故大都作为非结构胶使用。通过降低不饱和化学键含量、采用聚合收缩率低的单体、加入无机填料和热塑性高分子等手段,可以改善其整体性能。Unsaturated polyester resin: Unsaturated polyester is a linear resin made by reacting unsaturated dibasic acid (or anhydride) with partially saturated dibasic acid (or anhydride) and diol under the action of an initiator. polyester. There are unsaturated vinyl monomers in its molecular structure. If active vinyl monomers are used to copolymerize with such unsaturated vinyl monomers, they will be cross-linked and solidified to form a bulk structure. Generally speaking, the adhesive made of this resin has a large volume shrinkage during the curing process, and the internal stress of the glued joint is very large. Microcracks are prone to appear inside the adhesive layer, resulting in reduced adhesive force; at the same time, because the polymer chain contains ester bonds, it is easily hydrolyzed when encountering acid and alkali, so the medium resistance and water resistance are poor. It is easy to deform; in addition, its curing speed is slow, so it shows poor comprehensive performance, so it is mostly used as a non-structural adhesive. Its overall performance can be improved by reducing the content of unsaturated chemical bonds, using monomers with low polymerization shrinkage, adding inorganic fillers and thermoplastic polymers.

丙烯酸系树脂:该树脂体系固化速度快。丙烯酸系树脂包括聚酯-丙烯酸酯、环氧-丙烯酸酯、氨基甲酸酯-丙烯酸酯和聚醚-丙烯酸酯。Acrylic Resin: This resin system cures quickly. Acrylic resins include polyester-acrylates, epoxy-acrylates, urethane-acrylates and polyether-acrylates.

多硫醇-多烯体系为下列结构式的物质:The polythiol-polyene system is a substance of the following structural formula:

单体通常和树脂配合使用,一方面作为稀释剂,使胶液具有便于施工的粘度;另一方面又具有反应性,固化后进入树脂网络,对固化物的最终性能具有一定的改善。单体为苯乙烯、苯乙烯衍生物、单官能团丙烯酸酯或多官能团丙烯酸酯中的一种或多种的组合;单官能团或多官能团丙烯酸酯例如:甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙二醇酯、丙烯酸正丁酯等。The monomer is usually used in combination with the resin. On the one hand, it acts as a diluent to make the glue have a viscosity that is convenient for construction; on the other hand, it is reactive and enters the resin network after curing, which can improve the final performance of the cured product to a certain extent. The monomer is one or more combinations of styrene, styrene derivatives, monofunctional acrylate or multifunctional acrylate; monofunctional or multifunctional acrylate such as: methyl methacrylate, ethyl acrylate, acrylic acid Propylene glycol ester, n-butyl acrylate, etc.

对单体的要求主要是:低粘度、高稀释效果和高度的反应能力,同时还要兼顾挥发性、毒性和异味小,对树脂的相容性好等。The main requirements for monomers are: low viscosity, high dilution effect and high responsiveness, while also taking into account volatility, low toxicity and odor, and good compatibility with resins.

作为一种优选的方式,为了调节各种性能参数,采用混合单体,混合单体如下:自由基活性稀释剂和阳离子活性稀释剂。As a preferred manner, in order to adjust various performance parameters, mixed monomers are used, and the mixed monomers are as follows: free radical active diluent and cationic active diluent.

自由基活性稀释剂包括第一代丙烯酸多官能单体、第二代丙烯酸多官能单体和更优异的第三代丙烯酸单体。Free radical reactive diluents include first-generation acrylic polyfunctional monomers, second-generation acrylic polyfunctional monomers and more excellent third-generation acrylic monomers.

单官能活性稀释剂有:苯乙烯、N-乙烯基吡咯烷酮、丙烯酸异辛酯、丙烯酸羟乙酯和丙烯酸异冰片酯、甲基丙烯酸酯磷酸酯及甲基丙烯酸异冰片酯。Monofunctional reactive diluents are: styrene, N-vinylpyrrolidone, isooctyl acrylate, hydroxyethyl acrylate and isobornyl acrylate, methacrylate phosphate and isobornyl methacrylate.

双官能活性稀释剂有:三乙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、乙二醇二丙烯酸酯、聚乙二醇二丙烯酸醇酯、新戊二醇二丙烯酸酯和丙氧基新戊二醇二丙烯酸酯,丙烯酸酯官能单体有:1,6-己二醇二丙烯酸酯(HDDA)、1,4-丁二醇二丙烯酸酯(BDDA)、丙二醇二丙烯酸酯(DPGDA)、丙三醇二丙烯酸酯(TPGDA)、三官能团的三羟基甲基丙烷三丙烯酸酯(TMPTA)、季戊四醇三丙烯酸酯(PETA)、三羟基甲基丙烷三醇三丙烯酸酯(TMPTMA)、三羟甲基丙烷三丙烯酸酯、丙氧基化三羟基甲基丙烷三丙烯酸酯、季戊四醇三丙烯醇酯、丙氧基化季戊四醇丙烯醇酯、N,N-二羟乙基-3胺基丙酸甲酯、二缩三乙二醇双甲基丙烯酸酯、双季戊四醇五丙烯酸酯、二缩三丙二醇二丙烯酸酯、邻苯二甲酸二乙醇二丙烯酸酯(PDDA)。它们取代了活性小的第一代丙烯酸单官能单体。Difunctional reactive diluents are: triethylene glycol diacrylate, tripropylene glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, and propoxyneopentyl Diol diacrylate, acrylate functional monomers are: 1,6-hexanediol diacrylate (HDDA), 1,4-butanediol diacrylate (BDDA), propylene glycol diacrylate (DPGDA), propane Triol Diacrylate (TPGDA), Trifunctional Trimethylolpropane Triacrylate (TMPTA), Pentaerythritol Triacrylate (PETA), Trihydroxymethylpropane Triol Triacrylate (TMPTMA), Trimethylolpropane Triacrylate Propane Triacrylate, Propoxylated Trihydroxymethylpropane Triacrylate, Pentaerythritol Tripropenol, Propoxylated Pentaerythritol Propyl Ester, Methyl N,N-Dihydroxyethyl-3-Aminopropionate, Triethylene glycol dimethacrylate, dipentaerythritol pentaacrylate, tripropylene glycol diacrylate, phthalate diethanol diacrylate (PDDA). They replace less reactive first-generation acrylic monofunctional monomers.

第二代丙烯酸多官能单体主要是在分子中引入乙氧基或丙氧基,具有刺激性小、还具有更高的活性和固化程度。如乙氧基化三羟基甲基丙烷三醇三丙烯酸酯(TMP(EO)TMA)、丙氧基化三羟基甲基丙烷三醇三丙烯酸酯(TMP(PO)TMA)、丙氧基化丙三醇三丙烯酸酯(G(PO)TA)。The second-generation acrylic polyfunctional monomer mainly introduces ethoxy or propoxy groups into the molecule, which is less irritating and has higher activity and curing degree. Such as ethoxylated trimethylolpropane triol triacrylate (TMP(EO)TMA), propoxylated trimethylolpropane triol triacrylate (TMP(PO)TMA), propoxylated Triol Triacrylate (G(PO)TA).

第三代丙烯酸单体主要为含有甲氧基的丙烯酸酯,较好的解决了高固化速度与收缩率、低固化程度的矛盾。这类材料有1,6-己二醇甲氧基单丙烯酸酯(HDOMEMA)、乙氧基化新戊二醇甲氧基单丙烯酸酯(TMP(PO)MEDA)。分子中引入烷氧基后,可以降低单体的粘度,同时降低单体的刺激性。The third-generation acrylic monomer is mainly methoxy-containing acrylate, which better solves the contradiction between high curing speed, shrinkage rate and low curing degree. Such materials include 1,6-hexanediol methoxy monoacrylate (HDOMEMA), ethoxylated neopentyl glycol methoxy monoacrylate (TMP(PO)MEDA). After the alkoxy group is introduced into the molecule, the viscosity of the monomer can be reduced, and the irritation of the monomer can be reduced at the same time.

烷氧基的引入对稀释剂单体的相容性也有较大提高,乙烯基三乙氧基硅烷(A15I)、γ-甲基丙烯酰氧丙基三甲氧基硅烷(A174)可作为单体。The introduction of alkoxy groups also greatly improves the compatibility of diluent monomers. Vinyl triethoxysilane (A15I) and γ-methacryloxypropyl trimethoxysilane (A174) can be used as monomers .

各种活性环氧树脂稀释剂及各种环醚、环内酷、乙烯基醚单体等都可以作为阳离子活性稀释剂。其中乙烯基醚类化合物和低聚物固化速度快、粘度适中、无味、无毒,可以与环氧树脂配合使用。乙烯基醚单体有:三乙二醇二乙烯基醚(DVE-3)、1,4-丁二醇乙烯基醚(HBVE)、环己基乙烯基醚(CHVE)、全氟甲基乙烯基醚(PMVE)、全氟正丙基乙烯基醚、异丁基乙烯基醚、羟丁基乙烯基醚、乙烯基乙醚、乙基乙烯基醚、乙基乙烯基醚丙烯、乙二醇单烯丙基醚、羟丁基乙烯基醚、丁基乙烯基醚、三氟氯乙烯(CTFE)、三甘醇二乙烯基醚、乙烯基甲醚、乙烯基正丁醚、十二烷基乙烯基醚(DDVE)、环己基乙烯基醚、三苄基苯酚聚氧乙烯基醚、四氟乙烯-全氟丙基乙烯基醚、四氟乙烯-全氟丙基乙烯基醚、叔丁基乙烯基醚:Various reactive epoxy resin diluents and various cyclic ethers, lactones, vinyl ether monomers, etc. can be used as cationic reactive diluents. Among them, vinyl ether compounds and oligomers have fast curing speed, moderate viscosity, odorless and non-toxic, and can be used in conjunction with epoxy resin. Vinyl ether monomers include: triethylene glycol divinyl ether (DVE-3), 1,4-butanediol vinyl ether (HBVE), cyclohexyl vinyl ether (CHVE), perfluoromethyl vinyl ether Ether (PMVE), perfluoro-n-propyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, vinyl ethyl ether, ethyl vinyl ether, ethyl vinyl ether propylene, ethylene glycol monoene Propyl ether, hydroxybutyl vinyl ether, butyl vinyl ether, chlorotrifluoroethylene (CTFE), triethylene glycol divinyl ether, vinyl methyl ether, vinyl n-butyl ether, dodecyl vinyl Ether (DDVE), cyclohexyl vinyl ether, tribenzylphenol polyoxyethylene ether, tetrafluoroethylene-perfluoropropyl vinyl ether, tetrafluoroethylene-perfluoropropyl vinyl ether, tert-butyl vinyl ether ether:

环氧化合物单体有:3,4-环氧基环己基甲酸-3′、4′-环氧基环己基甲酯(ERL-4221)、双酚A型环氧树脂(EP)、环氧丙烯酸酯、环氧乙烯基酯、丙烯酸环氧酯、甲基丙烯酸环氧酯、水溶性衣康酸环氧酯树脂:Epoxy compound monomers include: 3,4-epoxycyclohexylcarboxylic acid-3′, 4′-epoxycyclohexylmethyl ester (ERL-4221), bisphenol A epoxy resin (EP), epoxy Acrylates, epoxy vinyl esters, epoxy acrylates, epoxy methacrylates, water soluble epoxy itaconate resins:

光引发剂:紫外光固化胶粘剂中,往往需要加入光活性化合物,以引发或加速反应的进行。按其作用机理的不同可以分为光引发剂和光敏剂。区别在于光引发剂在反应开始时,吸收适当波长及强度的光能,发生光物理过程达到其某一激发态,若该激发态能量大于断裂键所需要的能量,则产生自由基引发聚合;而光敏剂吸收光能至其某一激发态后,只是将能量在分子内或分子间进行转移,由获得能量的另一个分子产生自由基引发聚合。与光引发剂相比,光敏剂本身并不消耗或改变结构,它可以看作是光化学反应的催化剂。它的作用机理大致有三种:一是能量转移机理,二是夺氢机理,三是经生成电荷转移的光敏机理。已开发的具有实用价值的光引发剂有安息香及其衍生物和乙酰苯衍生物,光敏剂有二苯甲酮、硫杂蒽醌和米蚩酮。各种引发剂的稳定性、耐黄变性、引发速率各不相同,在不同的树脂体系中,引发效率也不一样,应根据不同场合的需要合理选用。如三烯丙基异氰脲酸酯和C(CH2OCCH2CH2SH)体系,分别用安息香甲醚、安息香乙醚,安息香异丙醚引发,固化时间分别为18s、20s、和25s,而用二苯甲酮引发时,固化时间仅为15s,同时固化物的透光率也会由于波长不同而差别较大,这要根据实际情况合理选用。Photoinitiator: In UV-curable adhesives, it is often necessary to add photoactive compounds to initiate or accelerate the reaction. According to their different mechanisms of action, they can be divided into photoinitiators and photosensitizers. The difference is that the photoinitiator absorbs light energy of appropriate wavelength and intensity at the beginning of the reaction, and a photophysical process occurs to reach a certain excited state. If the excited state energy is greater than the energy required to break the bond, free radicals will be generated to initiate polymerization; After the photosensitizer absorbs light energy to an excited state, it only transfers the energy within or between molecules, and another molecule that obtains energy generates free radicals to initiate polymerization. Compared with the photoinitiator, the photosensitizer itself does not consume or change the structure, and it can be regarded as a catalyst for photochemical reactions. There are roughly three mechanisms of action: one is the energy transfer mechanism, the other is the hydrogen abstraction mechanism, and the third is the photosensitive mechanism by generating charge transfer. The developed photoinitiators with practical value include benzoin and its derivatives and acetophenone derivatives, and the photosensitizers include benzophenone, thioxanthraquinone and Michler's ketone. The stability, yellowing resistance and initiation rate of various initiators are different. In different resin systems, the initiation efficiency is also different, so it should be selected reasonably according to the needs of different occasions. For example, triallyl isocyanurate and C(CH 2 OCCH 2 CH 2 SH) systems are initiated with benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether respectively, and the curing time is 18s, 20s, and 25s, respectively, while When triggered by benzophenone, the curing time is only 15s, and the light transmittance of the cured product will also vary greatly due to different wavelengths, which should be selected reasonably according to the actual situation.

光引发剂的作用是在其吸收紫外光能量后,经分解产生自由基,从而引发体系中的不饱和键聚合,交联固化成一个整体。常用的自由基型光引发剂有裂解型和提氢型两大类。The function of the photoinitiator is to generate free radicals through decomposition after absorbing ultraviolet light energy, thereby initiating the polymerization of unsaturated bonds in the system, and crosslinking and curing into a whole. Commonly used free radical photoinitiators include cracking type and hydrogen extraction type.

裂解型光引发剂:裂解型光引发剂主要有苯偶姻醚类(安息香醚类)、苯偶酰缩酮和苯乙酮等。裂解型光引发剂在吸收紫外光后皲裂,产生两个自由基,自由基引发不饱和基团聚合。苯偶姻醚类(安息香醚类)包括:安息香(Benzoin)、安息香甲醚、安息香乙醚(Benzoinethylether)、安息香丁醚(Benzoinbutylether)、安息香亏(Benzoinoxime)、安息香异丙醚;酰基膦氧化物包括:2,4,6三甲基苯甲酰二苯基氧膦(TPO)和(2,4,6-三甲基苯甲酰)苯基氧化膦[BAPOphenylbis(2,4,6-trimethylbenzoyl)phosphineoxide]、苯基双(2,4,6-三甲基苯甲酰基)氧化膦(819)、四甲基哌啶酮氧化物(TMPO)、磷酸三乙酯(TEPO),它们是比较理想的光引发剂,具有很高的光引发活性,对长波近紫外线有吸收,适用于白色涂料和膜较厚的情况,而且具有很好的稳定性,不会变色或褪色。Cleavage-type photoinitiators: Cleavage-type photoinitiators mainly include benzoin ethers (benzoin ethers), benzil ketals, and acetophenones. The cleavage-type photoinitiator cracks after absorbing ultraviolet light, generating two free radicals, which initiate the polymerization of unsaturated groups. Benzoin ethers (benzoin ethers) include: benzoin, benzoin methyl ether, benzoinethylether, benzoinbutylether, benzoinoxime, benzoin isopropyl ether; acylphosphine oxides include : 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO) and (2,4,6-trimethylbenzoyl)phenylphosphine oxide [BAPOphenylbis (2,4,6-trimethylbenzoyl) phosphineoxide], phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (819), tetramethylpiperidone oxide (TMPO), triethyl phosphate (TEPO), they are ideal It is a photoinitiator with high photoinitiation activity and absorbs long-wave near-ultraviolet rays. It is suitable for white paints and thick films, and has good stability without discoloration or fading.

提氢型引发剂:提氢型引发剂主要有二苯甲酮类和硫杂蒽酮类等。其中硫杂蒽酮类光引发剂在近紫外光区的最大吸收波长在380-420nm,且吸收能力和夺氢能力强,具有较高的引发效率。提氢型引发剂必须要有供氢体作为协同成份,否则,引发效率太低,以至不能付诸应用。三线态羰基游离基从供氢体分子的三级碳上比二级碳上或甲基上更有可能提取氢,接在氧或氮等杂原子上的氢比碳原子上的氢更易提取。这类供氢体有胺、醇胺(三乙醇胺、甲基二乙醇胺、三异丙醇胺等)、硫醇、N,N-二乙基-对二甲氨基苯甲酰胺。Hydrogen-extracting initiators: Hydrogen-extracting initiators mainly include benzophenones and thioxanthones. Among them, the thioxanthone photoinitiator has a maximum absorption wavelength of 380-420nm in the near-ultraviolet region, has strong absorption capacity and hydrogen abstraction capacity, and has high initiation efficiency. The hydrogen-extracting initiator must have a hydrogen donor as a synergistic component, otherwise, the initiation efficiency is too low to be put into practice. The triplet carbonyl radical is more likely to extract hydrogen from the tertiary carbon of the hydrogen donor molecule than the secondary carbon or methyl group, and the hydrogen attached to heteroatoms such as oxygen or nitrogen is easier to extract than the hydrogen on carbon atoms. Such hydrogen donors include amines, alcohol amines (triethanolamine, methyldiethanolamine, triisopropanolamine, etc.), mercaptans, and N,N-diethyl-p-dimethylaminobenzamide.

二苯酮光引发体系,二苯酮需要与醇、醚或胺并用才能使烯类单体进行光聚合。主要包括:二苯甲酮、硫杂蒽醌、米蚩酮、二甲氧基苯甲基苯基酮(DMPA)、α-羟基-2,2二甲基苯乙酮(1173)、α-羟基环己基苯基酮(184)、α-胺烷基苯酮、2-甲基-1(4-甲琉基苯基)-2-吗啉基丙酮(MMMP)、2’2-二苯甲酰氨基二苯基二硫化物(DBMD)、(4-二甲氨基苯基)-(1-哌啶基)-甲酮、异丙基硫杂蒽酮(ITX)、(4-二甲氨基苯基)-(4-吗啉基)-甲酮、2-羟基-2-甲基-1-苯基-1-苯基-1-丙酮、二苯氧基二苯酮、羟基-2-甲基苯基丙烷-1-酮。以及混合体系,如可消除胶膜中的氧气对自由基聚合反应的阻聚作用的二苯甲酮与叔氨的配合引发剂体系;米蚩酮和二苯甲酮配合使用,可得到较便宜和很有效的引发剂体系。Benzophenone photoinitiation system, benzophenone needs to be used in combination with alcohol, ether or amine to make vinyl monomers photopolymerize. Mainly include: benzophenone, thioxanthraquinone, Michler's ketone, dimethoxybenzyl phenyl ketone (DMPA), α-hydroxy-2,2 dimethylacetophenone (1173), α- Hydroxycyclohexylphenylketone (184), α-aminoalkylphenone, 2-methyl-1(4-methylmercaptophenyl)-2-morpholinoacetone (MMMP), 2'2-diphenyl Formamidodiphenyl disulfide (DBMD), (4-dimethylaminophenyl)-(1-piperidinyl)-methanone, isopropylthioxanthone (ITX), (4-dimethyl Aminophenyl)-(4-morpholinyl)-methanone, 2-hydroxy-2-methyl-1-phenyl-1-phenyl-1-propanone, diphenoxybenzophenone, hydroxy-2 -Methylphenylpropan-1-one. And mixed systems, such as the coordinated initiator system of benzophenone and tertiary ammonia that can eliminate the inhibition of oxygen in the film to free radical polymerization; Michler's ketone and benzophenone are used in conjunction to obtain cheaper and very effective initiator system.

阳离子型光引发剂:芳香硫鎓盐和碘鎓盐类引发剂具有优异的高温稳定性,与环氧树脂配合后也具有稳定性,所以被广泛应用于阳离子固化体系。但它们的最长吸收波长在远紫外区,在近紫外区没有吸收,一般要添加光增感剂,如:自由基引发剂或光敏染料进行增感。Cationic photoinitiator: Aromatic sulfonium salt and iodonium salt initiators have excellent high temperature stability and are also stable when combined with epoxy resin, so they are widely used in cationic curing systems. However, their longest absorption wavelength is in the far ultraviolet region, and there is no absorption in the near ultraviolet region. Generally, photosensitizers, such as free radical initiators or photosensitizing dyes, are added for sensitization.

此类引发剂包括:二甲苯基碘六氟磷酸盐(PI810)、羟基苯基碘鎓盐(HTIB)、4,4-双十二烷基苯碘鎓六氟锑酸盐、二甲苯基碘鎓盐、二苯基六氟砷酸碘鎓盐、[4-(2-羟基-3-丁氧基-1-丙氧基)苯基]苯碘鎓-六氟锑酸盐、[4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、[4-(4-苯甲酰基苯氧基)苯]苯基碘鎓六氟磷酸盐、4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、4,4′-二甲基二苯基碘鎓盐六氟磷酸盐(IHT-PI820)、4,4′二乙酰胺基二苯基碘六氟磷酸盐、3,7一二硝基二苯并环状碘鎓盐及3,7一二硝基二苯并环状溴鎓盐、四氟硼酸二芳基碘鎓盐、3,3′-二硝基二苯基碘鎓盐、3,3′-二硝基二苯基碘鎓盐和几种2,2′-二取代(碘、溴、氯)-5,5′-二硝基苯基碘鎓盐、碘化2-[2-(3-中氮茚)乙烯基]-1-甲基喹啉鎓盐、碘化4-(2-苯并噁唑)-N-甲基吡啶鎓盐、3-硝基苯基二苯基硫六氟磷酸盐、三芳基膦二氢咪唑鎓盐、三芳基膦1,1′-联萘二氢咪唑环鎓盐、3,7-二硝基二苯并溴五环盐、对甲基苯磺酸三苯基硫鎓盐、溴化三苯基硫鎓盐、(4-苯硫基-苯基)二苯基硫鎓六氟磷酸盐、4-(苯硫基)三苯基硫鎓六氟磷酸盐、3,3′-二硝基二苯基碘六氟磷酸盐、3-硝基苯基二苯基硫六氟磷酸盐、三苯基硫鎓盐、4-氯苯基二苯基硫六氟磷酸盐、3-硝基苯基二苯基硫六氟磷酸盐、4-乙酰胺基苯基二苯基硫六氟磷酸盐、3-苯甲酰基苯基二苯基硫六氟磷酸盐、三苯基硫氟硼酸盐、三苯基硫六氟磷酸盐、三苯基硫六氟锑酸盐、4-甲苯基二苯基硫六氟磷酸盐、六氟化磷三芳基硫鎓盐、六氟化锑三芳基硫鎓盐、[4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、1-(4′-溴-2′-氟苄基)吡啶鎓盐、[4-(对苯甲酰基苯硫基)苯]苯基碘鎓六氟磷酸盐、{4-[4-(对硝基苯甲酰基)苯硫基]苯}苯基碘鎓六氟磷酸盐、{4-[4-(对甲基苯甲酰基)苯硫基]苯}苯基碘鎓六氟磷酸盐、{4-[4-(对甲基苯甲酰基)苯氧基]苯}苯基碘鎓六氟磷酸盐、[4-(对苯甲酰基苯氧基)苯]苯基碘鎓六氟磷酸盐、4,4-双十二烷基苯碘鎓六氟锑酸盐。Such initiators include: xylyl iodide hexafluorophosphate (PI810), hydroxyphenyl iodonium salt (HTIB), 4,4-didodecylphenyliodonium hexafluoroantimonate, xylyl iodide Onium salt, iodonium diphenylhexafluoroarsenate, [4-(2-hydroxy-3-butoxy-1-propoxy)phenyl]phenyliodonium-hexafluoroantimonate, [4- (p-benzoylphenylthio)phenyl]phenyliodonium hexafluorophosphate, [4-(4-benzoylphenoxy)phenyl]phenyliodonium hexafluorophosphate, 4-(p-benzoylphenoxy Acylphenylthio)phenyl]phenyliodonium hexafluorophosphate, 4,4′-dimethyldiphenyliodonium hexafluorophosphate (IHT-PI820), 4,4′diacetamidodiphenyl Iodide hexafluorophosphate, 3,7-dinitrodibenzocyclic iodonium salt and 3,7-dinitrodibenzocyclic bromide salt, tetrafluoroborate diaryliodonium salt, 3 , 3′-dinitrodiphenyliodonium salt, 3,3′-dinitrodiphenyliodonium salt and several 2,2′-disubstituted (iodo, bromo, chloro)-5,5′ -Dinitrophenyliodonium salt, 2-[2-(3-indolizine)vinyl]-1-methylquinolinium iodide, 4-(2-benzoxazole) iodide- N-methylpyridinium salt, 3-nitrophenyldiphenylthiohexafluorophosphate, triarylphosphine dihydroimidazolium salt, triarylphosphine 1,1'-binaphthyl dihydroimidazolium salt, 3 , 7-Dinitrodibenzobromopentacyclic salt, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium bromide, (4-phenylthio-phenyl) diphenylsulfide Onium hexafluorophosphate, 4-(phenylthio)triphenylsulfonium hexafluorophosphate, 3,3′-dinitrodiphenyliodohexafluorophosphate, 3-nitrophenyldiphenylsulfur Hexafluorophosphate, triphenylsulfonium salt, 4-chlorophenyldiphenylthiohexafluorophosphate, 3-nitrophenyldiphenylthiohexafluorophosphate, 4-acetamidophenyldiphenyl Triphenylthiohexafluorophosphate, 3-benzoylphenyldiphenylthiohexafluorophosphate, triphenylthiofluoroborate, triphenylthiohexafluorophosphate, triphenylthiohexafluoroantimonate , 4-tolyldiphenylthiohexafluorophosphate, phosphorus hexafluoride triarylsulfonium salt, antimony hexafluoride triarylsulfonium salt, [4-(p-benzoylphenylthio)phenyl]phenyl Ionium hexafluorophosphate, 1-(4'-bromo-2'-fluorobenzyl)pyridinium salt, [4-(p-benzoylphenylthio)phenyl]phenyliodonium hexafluorophosphate, { 4-[4-(p-Nitrobenzoyl)phenylthio]phenyl}phenyliodonium hexafluorophosphate, {4-[4-(p-methylbenzoyl)phenylthio]phenyl}phenyl Ionium hexafluorophosphate, {4-[4-(p-methylbenzoyl)phenoxy]phenyl}phenyliodonium hexafluorophosphate, [4-(p-benzoylphenoxy)benzene] Phenyliodonium hexafluorophosphate, 4,4-didodecylphenyliodonium hexafluoroantimonate.

茂铁盐类:茂铁盐类光引发体系是继二芳香碘鎓盐和三芳香硫鎓盐后发展的一种新阳离子光引发剂,在光照下茂铁盐离子首先形成芳香基配位体,同时产生与一个环氧化合物分子配位的不饱和铁的络合物,此络合物具路易斯酸的特点并接着形成与三个环氧化合物分子配位的络合物,其中一个环氧化合物可开环形成阳离子,它能引发阳离子开环聚合反应,形成聚合物。在常温下由于二茂铁盐-环氧基配合物、环氧化合物阳离子活性种的形成需要时间,故需在外界加热的条件下,以提高聚合速度。Ferrocene salts: Ferrocene salts photoinitiation system is a new cationic photoinitiator developed after diaromatic iodonium salts and triaromatic sulfonium salts. Ferrocene salt ions first form aromatic ligands under light , simultaneously producing an unsaturated iron complex coordinated to one epoxy compound molecule, which has the characteristics of a Lewis acid and subsequently forms a complex coordinated to three epoxy compound molecules, one of which is The compound can be ring-opened to form a cation, which can initiate cationic ring-opening polymerization to form a polymer. Since the formation of ferrocene salt-epoxy complexes and epoxy compound cationic active species takes time at room temperature, it is necessary to increase the polymerization rate under the condition of external heating.

此类盐类包括:环戊二烯基-铁-苯盐、环戊二烯基-铁-甲苯盐、环戊二烯基-铁-对二甲苯盐、环戊二烯基-铁-萘盐、环戊二烯基-铁-联苯盐、环戊二烯基-铁-2,4-二甲基苯乙酮盐、乙酰基-环戊二烯基-铁-对二甲苯盐、环戊二烯基-铁-苯甲醚盐、环戊二烯基-铁-二苯醚盐、环戊二烯基-铁-2,4-二乙氧基苯盐、二茂铁四氟硼酸盐、甲苯茂铁四氟硼酸盐、环戊二烯基-铁-苯甲醚盐、环戊二烯基-铁-二苯醚盐、环戊二烯基-铁-1,4-二乙氧基苯盐、环戊二烯基-铁-氯苯盐、环戊二烯基-铁-(1,4-二乙氧基苯)六氟磷酸盐、环戊二烯基-铁-二苯醚六氟磷酸盐、1,10-邻二氮杂菲高氯酸亚铁盐、1,10-邻二氮杂菲硫酸亚铁盐环戊二烯基-铁-苯甲醚盐、环戊二烯基-铁-二苯醚盐、[1,1′-双(二苯基膦)二茂铁]二氯化镍、乙烯基二茂铁、N,N′-双二茂铁亚甲基丁二胺季铵盐、二茂铁甲酰胺、二茂铁酰基丙酸、乙酰基二茂铁、乙基二茂铁,丁酰基二茂铁,丁基二茂铁,N,N-二甲基-胺甲基二茂铁、1,1′-二苯甲酰基二茂铁、(3-羧丙酰基)二茂铁、1,1′-二溴二茂铁、氨基二茂铁。Such salts include: Cyclopentadienyl-Iron-Benzene Salt, Cyclopentadienyl-Iron-Toluene Salt, Cyclopentadienyl-Iron-P-Xylene Salt, Cyclopentadienyl-Iron-Naphthalene salt, cyclopentadienyl-iron-biphenyl salt, cyclopentadienyl-iron-2,4-dimethylacetophenone salt, acetyl-cyclopentadienyl-iron-p-xylene salt, Cyclopentadienyl-iron-anisole salt, cyclopentadienyl-iron-diphenyl ether salt, cyclopentadienyl-iron-2,4-diethoxyphenyl salt, ferrocenetetrafluoro Borate, tolyl ferrocene tetrafluoroborate, cyclopentadienyl-iron-anisole salt, cyclopentadienyl-iron-diphenyl ether salt, cyclopentadienyl-iron-1,4 -diethoxybenzene salt, cyclopentadienyl-iron-chlorobenzene salt, cyclopentadienyl-iron-(1,4-diethoxybenzene) hexafluorophosphate, cyclopentadienyl- Iron-diphenyl ether hexafluorophosphate, 1,10-phenanthrene perchlorate, ferrous sulfate, cyclopentadienyl-iron-anisole salt, cyclopentadienyl-iron-diphenyl ether salt, [1,1′-bis(diphenylphosphino)ferrocene]nickel dichloride, vinylferrocene, N,N′-bis Ferrocene methylene butanediamine quaternary ammonium salt, ferrocene formamide, ferrocenyl propionic acid, acetyl ferrocene, ethyl ferrocene, butyryl ferrocene, butyl ferrocene, N, N-Dimethyl-aminomethylferrocene, 1,1′-dibenzoylferrocene, (3-carboxypropionyl)ferrocene, 1,1′-dibromoferrocene, amino di Ferrocene.

高分子负载的光引发剂:光固化体系中,光引发剂在光固化过程中往往不是完全耗尽,未光解的部分会迁移到涂层表面,使涂层泛黄和老化,影响产品的质量;另一方面,一些引发剂和体系不相容或相容性不好,使其应用受到限制。为解决这些问题,人们将光引发剂高分子化。高分子化的引发剂相对低分子的引发剂具有如下优点:A、在聚合物链中能量迁移和分子间反应变得更加容易,使高分子光引发剂具有更高的活性。B、通过与非活性基团共聚,调节并设计光敏基团的距离,或改变光活性基团与主链的距离,从而获得具有不同光活性的引发剂。C、可以在同一高分子链引入不同的光活性基团,利用它们的协同效应来提高光敏效应。D、引发剂的高分子化,限制了引发剂的迁移,防止涂层变黄和老化。E、由于大多数光解碎片仍连在高分子基体上,因此,可以降低体系的气味和毒性。Polymer-loaded photoinitiator: In the photocuring system, the photoinitiator is often not completely exhausted during the photocuring process, and the unphotolyzed part will migrate to the surface of the coating, making the coating yellow and aging, affecting the quality of the product. quality; on the other hand, some initiators and systems are not compatible or have poor compatibility, which limits their application. In order to solve these problems, people polymerize the photoinitiator. Compared with low-molecular initiators, high-molecular initiators have the following advantages: A. Energy migration and intermolecular reactions in the polymer chain become easier, making the high-molecular photoinitiator more active. B. By copolymerizing with inactive groups, adjusting and designing the distance of photosensitive groups, or changing the distance between photoactive groups and the main chain, so as to obtain initiators with different photoactivities. C. Different photoactive groups can be introduced into the same polymer chain, and their synergistic effect can be used to improve the photosensitive effect. D. The polymerization of the initiator limits the migration of the initiator and prevents the coating from yellowing and aging. E. Since most photolytic fragments are still connected to the polymer matrix, the odor and toxicity of the system can be reduced.

引发剂的高分子化可以将引发剂直接连在高分子或低聚物的链上,如将硫杂蒽酮或酸基氧化膦等引入高分子链上;也可以在引发剂中引入可以发生聚合的官能团,使其在光固化过程中实现高分子化,如将二苯甲酮结构引入四丙烯酸酯中。The polymerization of the initiator can directly connect the initiator to the chain of the polymer or oligomer, such as introducing thioxanthone or acid group phosphine oxide into the polymer chain; it can also be introduced into the initiator. The polymerized functional group enables it to achieve polymerization during the photocuring process, such as introducing the benzophenone structure into tetraacrylate.

各种光引发剂的配伍也是近年来的一个研究方向,经过配伍后再使用,既可以降低成本,又可以扩大吸收波长的区域,提高紫外光辐射能量的吸收,从而获得好的固化效果。光引发剂的配伍既可以是同一类型之间,如同是自由基型的,例如Ciba新推出的Irgacure-1700就是由25%的(2,4,6-三甲基苯甲酰)苯基氧化膦(BAPO)和75%的α-羟基-2,2二甲基苯乙酮(1173)组成,Irgacure-1800就是由25%的BAPO和75%的α-羟基环己基苯基酮(184)组成等;也可以是由不同类型的引发剂组成,如自由基型的和阳离子型的光引发剂配伍,例如,将三芳基硫蒽盐和二苯甲酮配合,可以使环氧化合物的固化速度得到提高。The compatibility of various photoinitiators is also a research direction in recent years. After compatibility, it can not only reduce the cost, but also expand the absorption wavelength area, improve the absorption of ultraviolet radiation energy, and obtain a good curing effect. The compatibility of photoinitiators can be between the same type, as free radical type, for example, Ciba's new Irgacure-1700 is oxidized by 25% (2,4,6-trimethylbenzoyl)phenyl Phosphine (BAPO) and 75% α-hydroxy-2,2 dimethylacetophenone (1173), Irgacure-1800 is composed of 25% BAPO and 75% α-hydroxycyclohexyl phenyl ketone (184) Composition, etc.; it can also be composed of different types of initiators, such as the combination of free radical and cationic photoinitiators, for example, the combination of triarylsulfanthracene salt and benzophenone can make the curing of epoxy compounds Speed is improved.

助剂:一般来说,为适应不同环境的粘结要求,紫外光固化胶粘剂中还需要加入各种助剂,如增塑剂、触变剂、填充剂、防静电剂、阻燃剂、偶联剂等。它们在胶粘剂中所占的分量虽然不多,有时却对胶的加工性能或粘结性能产生至关重要的作用。如三烯丙基异氰脲酸酯和C(CH2OCCH2CH2SH)在二苯甲酮的引发下,若加入l%的硅偶联剂CH2=CHSi(OCH2CH2OCH3)3,经紫外光固化后,置于80-100%湿度的环境下,一年后未发现变化,而若不加偶联剂,相同条件下,2日后粘结部位便发生白蚀,一周后胶层完全剥离下来。Auxiliaries: Generally speaking, in order to meet the bonding requirements of different environments, various auxiliaries need to be added to UV-curable adhesives, such as plasticizers, thixotropic agents, fillers, antistatic agents, flame retardants, occasional Joint agent, etc. Although they account for a small amount in the adhesive, sometimes they play a vital role in the processing performance or bonding performance of the glue. For example, if triallyl isocyanurate and C(CH 2 OCCH 2 CH 2 SH) are triggered by benzophenone, if 1% silicon coupling agent CH 2 =CHSi(OCH 2 CH 2 OCH 3 ) 3. After being cured by ultraviolet light and placed in an environment with a humidity of 80-100%, no change is found after one year. If no coupling agent is added, under the same conditions, white etching will occur at the bonding part after 2 days, and after a week The back glue layer is completely peeled off.

增塑剂包括:壬二酸二异辛酯(DIOZ)、壬二酸二辛酯(DOZ)、邻苯二甲酸二已酯(DHP)、暌二酸二辛酯(DOS)、已二酸二辛酯(DOA)、邻苯二甲酸二异丁酯(DIBP)、邻苯二甲酸二辛酯(DOP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二丙酯(DAP)、三丁氧基乙烯基磷酸酯、聚乙烯醇缩丁醛、乙酰柠檬酸三丁酯、邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)、已二酸二(丁氧基乙氧基)乙酯、钛酸异丙酯、钛酸正丁酯、柠檬酸三乙酯、柠檬酸三丁酯、乙酰柠檬酸三丁酯、偏苯三酸三(2-乙基)己酯(TOTM)、邻苯二甲酸二(2-乙基)己酯、癸二酸二(2-乙基)己酯(DOS)、一缩二乙二醇二苯甲酸酯(DEDB)、邻苯二甲酸酐、二丙二醇二苯甲酸酯、暌二酸二苄酯(DBS)、硬脂酸正丁酯(BS)、氯磺化聚乙烯(增韧弹性体)、磷酸三苯酯(TPP)、磷酸三(二甲苯)酯(TXP)、聚已二酸亚丙基酯(PPA)、环氧大豆油(ESO)、环氧硬脂酸辛酯(OES2)、氯化石蜡-42(CP-42)、氯化石蜡-48(CP-48)、氯化石蜡-52(CP-52)、二硬脂酸二甘醇(DEDR)、磷酸三苯甲酯(TCP)、磷酸二苯辛酯(DPO)、聚已二酸亚丁基酯(PBA)、环氧硬脂酸丁酯(BES)、氯代联苯(CDP)、二甲苯缩甲醛树脂(增塑剂FH)、轻石蜡型基础油(PROCESSOIL637)、大豆油、环烷类加工油(310)、W150软化油(石油碳氢化合物,氢化合成油)、锆铝系偶合剂、WB215(脂肪酸18%;脂肪酸脂52%;碳酸钙20%)。Plasticizers include: diisooctyl azelate (DIOZ), dioctyl azelate (DOZ), dihexyl phthalate (DHP), dioctyl azelate (DOS), adipic acid Dioctyl phthalate (DOA), diisobutyl phthalate (DIBP), dioctyl phthalate (DOP), dibutyl phthalate (DBP), dipropyl phthalate (DAP) ), tributoxyvinyl phosphate, polyvinyl butyral, acetyl tributyl citrate, dimethyl phthalate (DMP), diethyl phthalate (DEP), adipic acid Bis(butoxyethoxy)ethyl ester, isopropyl titanate, n-butyl titanate, triethyl citrate, tributyl citrate, acetyl tributyl citrate, trimellitic acid tri(2 -Ethyl)hexyl (TOTM), Di(2-ethyl)hexyl phthalate, Di(2-ethyl)hexyl sebacate (DOS), Diethylene glycol dibenzoate Esters (DEDB), Phthalic Anhydride, Dipropylene Glycol Dibenzoate, Dibenzyl Sulfate (DBS), n-Butyl Stearate (BS), Chlorosulfonated Polyethylene (toughened elastomer) , Triphenyl Phosphate (TPP), Tris(xylene) Phosphate (TXP), Polypropylene Adipate (PPA), Epoxy Soybean Oil (ESO), Epoxy Octyl Stearate (OES2), Chlorinated paraffin-42 (CP-42), chlorinated paraffin-48 (CP-48), chlorinated paraffin-52 (CP-52), diethylene glycol distearate (DEDR), trityl phosphate ( TCP), diphenyloctyl phosphate (DPO), polybutylene adipate (PBA), butyl epoxy stearate (BES), chlorinated biphenyl (CDP), xylene formal resin (plasticized agent FH), light paraffinic base oil (PROCESSOIL637), soybean oil, naphthenic processing oil (310), W150 softening oil (petroleum hydrocarbons, hydrogenated synthetic oil), zirconium-aluminum coupling agent, WB215 (fatty acid 18% ; fatty acid lipid 52%; calcium carbonate 20%).

偶联剂是一类具有两性结构的物质,它们分子中的一部分基团可与无机物表面的化学基团反应,形成强固的化学键合;另一部分基团则有亲有机物的性质,可与有机分子反应或物理缠绕,从而把两种性质大小不同的材料牢固结合起来。目前工业上使用的偶联剂按化学结构分为硅烷类、酰酸酯类、锆类和有机铬络合物四大类。其中在胶粘剂中应用较多的是硅烷类,如甲基乙烯基二氯硅烷、甲基氢二氯硅烷、二甲基二氯硅烷、二甲基一氯硅烷、乙烯基三氯硅烷、γ-氨丙基三甲氧基硅烷、聚二甲基硅氧烷、聚氢甲基硅氧烷、聚甲基甲氧基硅氧烷、γ-甲基丙烯酸丙醋基三甲氧基硅烷(KH-570)、γ-氨丙基三乙氧基硅烷(KH-550)、γ-缩水甘油醚丙基三甲氧基硅烷、氨丙基倍半硅氧烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、长链烷基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、γ-氯丙基三乙氧基硅烷、双-(γ-三乙氧基硅基丙基)、苯胺甲基三乙氧基硅烷、N-β(氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、N-β(氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-(2,3-环氧丙氧)丙基三甲氧基硅烷、γ-(甲基丙烯酰氧)丙基三甲基硅烷、γ-巯基丙基三甲氧基硅烷、γ-巯基丙基三乙氧基硅烷。Coupling agents are substances with an amphoteric structure. Some groups in their molecules can react with chemical groups on the surface of inorganic substances to form strong chemical bonds; Molecular reaction or physical entanglement, so that two materials with different properties and sizes are firmly combined. The coupling agents currently used in industry are divided into four categories according to their chemical structures: silanes, acyl esters, zirconiums and organic chromium complexes. Among them, silanes are more widely used in adhesives, such as methyl vinyl dichlorosilane, methyl hydrogen dichlorosilane, dimethyl dichlorosilane, dimethyl monochlorosilane, vinyl trichlorosilane, γ- Aminopropyltrimethoxysilane, Polydimethylsiloxane, Polyhydromethylsiloxane, Polymethylmethoxysiloxane, Gamma-Propyltrimethoxysilane Methacrylate (KH-570 ), γ-aminopropyl triethoxysilane (KH-550), γ-glycidyl ether propyl trimethoxysilane, aminopropyl silsesquioxane, γ-methacryloxypropyl trimethyl Oxysilane, long-chain alkyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-chloropropyltriethoxysilane, bis-(γ-triethoxysilyl Propyl), anilinomethyltriethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxy N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-(2,3-glycidyloxy)propyltrimethoxysilane, γ-(methacrylic Acyloxy)propyltrimethylsilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane.

流平剂是用来改善树脂的流平性能,防止缩孔和针眼等涂层弊病的产生,使涂膜平整,并可以提高光泽度,包括混合溶剂、有机硅、聚丙烯酸酯、醋酸丁酸纤维、硝化纤维素和聚乙烯醇缩丁醛。其中有机硅类,包含二苯基聚硅氧烷、甲基苯基聚硅氧烷、有机基改性聚硅氧烷、聚醚有机硅。The leveling agent is used to improve the leveling performance of the resin, prevent the occurrence of coating defects such as shrinkage and pinholes, make the coating film smooth, and improve the gloss, including mixed solvents, silicone, polyacrylate, acetic acid butyric acid Fiber, nitrocellulose and polyvinyl butyral. Among them, silicones include diphenyl polysiloxane, methylphenyl polysiloxane, organo-modified polysiloxane, and polyether silicone.

稳定剂是用来减少存放时发生聚合,提高树脂的存储稳定性。常用的稳定剂有对苯二酚、对甲氧基苯酚、对苯醌、2,6一二叔丁基甲苯酚、酚噻嗪、蒽醌等。Stabilizers are used to reduce polymerization during storage and improve the storage stability of the resin. Commonly used stabilizers include hydroquinone, p-methoxyphenol, p-benzoquinone, 2,6-di-tert-butylcresol, phenothiazine, anthraquinone, etc.

消泡剂是用来防止和消除涂料在制造和使用过程中产生气泡,防止涂层产生针眼等弊病。磷酸酯、脂肪酸酯和有机硅等都可以作消泡剂。具体有磷酸三丁酯、磷酸二丁酯、磷酸酯抑泡剂(AD-14L)、消泡王(FAG470)、消泡剂(FAG470)、消泡剂(BYK-141)、消泡剂(BYK037)、三(丁氧基乙基)磷酸酯、三乙基磷酸酯、三丁基磷酸酯、磷酸三乙酯、磷酸三氯异丙基酯、磷酸三丁氧基乙基酯、聚氧丙烯聚氧乙烯和二醇或三醇醚的混合体(浅黄色至无色透明粘稠液体)、聚二甲基硅氧烷、甘油聚氧丙烯醚(GP330)、月桂醇聚醚、聚氧乙烯聚氧丙烯季戊四醇醚、聚氧乙烯聚氧丙醇胺醚、聚氧丙烯甘油醚和聚氧丙烯、聚醚、聚乙二醇脂肪酸酯、硬脂酸金属皂、聚脲、高碳醇脂肪酸酯复合物;有机硅消泡剂有聚醚改性有机硅氧烷、有机聚硅氧烷混合物、乳化硅油。The defoaming agent is used to prevent and eliminate the bubbles generated during the manufacture and use of the coating, and to prevent the coating from producing pinholes and other ills. Phosphate esters, fatty acid esters, and silicones can all be used as defoamers. Specifically, there are tributyl phosphate, dibutyl phosphate, phosphate ester foam inhibitor (AD-14L), defoamer king (FAG470), defoamer (FAG470), defoamer (BYK-141), defoamer ( BYK037), tri(butoxyethyl) phosphate, triethyl phosphate, tributyl phosphate, triethyl phosphate, trichloroisopropyl phosphate, tributoxyethyl phosphate, polyoxygen Mixture of propylene polyoxyethylene and glycol or triol ether (light yellow to colorless transparent viscous liquid), polydimethylsiloxane, glycerol polyoxypropylene ether (GP330), lauryl ether, polyoxyethylene Ethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropanolamine ether, polyoxypropylene glyceryl ether and polyoxypropylene, polyether, polyethylene glycol fatty acid ester, stearic acid metal soap, polyurea, high carbon alcohol Fatty acid ester complexes; silicone defoamers include polyether-modified organosiloxane, organopolysiloxane mixture, and emulsified silicone oil.

阻聚剂是用来减少存放时发生聚合,提高树脂的存储稳定性。常用的阻聚剂一般分为分子型阻聚剂和稳定自由基型阻聚剂,前者主要有:对苯二酚、对苯醌、酚噻嗪、β-苯基萘胺、对叔丁基邻苯二酚、亚甲基蓝、三(N-亚硝基-N-苯基羟胺)铝盐、氯化亚铜、三氯化铁等无机物以及硫黄等也可作阻聚剂稳定自由基型阻聚剂主要有1,1-二苯基-2-苦肼(DPPH)、2,2,6,6-四甲基哌啶氮氧自由基(TMP)、对苯二酚、乙酸烯丙酯、对羟基苯甲醚(MEHQ)、氮氧自由基哌啶醇、亚磷酸(2,2,6,6-四甲基哌啶氮氧自由基)混合酯、4-羟基-2,2,6,6-四甲基哌啶-1-氧自由基(TMHPHA)、8%三(N-亚硝基-N-苯基羟胺)铝盐:92%的2-酚基乙氧基丙烯酸酯、4%三(N-亚硝基-N-苯基羟胺)铝盐、96%乙氧基单油三丙烯酸酯、氢醌甲基醚、阻聚剂铜盐、邻甲基对苯二酚、2,6-二叔丁基甲苯酚、二甲基对苯二酚、对叔丁基邻苯二酚(TBC)、邻苯二酚、对甲氧基苯酚、2.6-二叔丁基对甲酚、2.5-二叔丁基对苯二酚、对苯醌、甲基氢醌、1.4-萘醌,吩噻嗪、叔丁基对苯二酚(TBHQ)、邻仲丁基-4,6二硝基苯酚(DNBP)、乙二醇单丙醚、烷基苯磺酸胺盐、对-特丁基邻苯二酚、甲基丙烯酸甲酯(MMA)、2,4,6-三硝基苯酚(TNP)、2,4-二甲基-6-叔丁基苯酚(TBX)、N,N-二乙基羟胺(DEHA)、对特丁基邻苯二酚、2,5-二特丁基对苯二酚、邻甲基对苯二邻甲基对苯醌、3-特丁基-4-羟基苯甲醚(BHA)、2,6-二硝基对甲酚(DNPC)、聚乙烯醇缩乙醛、氮氧自由基哌啶醇、4,6-二硝基邻仲丁基酚、丁二酰丁二酸二甲酯(DMSS)、丙炔醇。The polymerization inhibitor is used to reduce the polymerization during storage and improve the storage stability of the resin. Commonly used polymerization inhibitors are generally divided into molecular inhibitors and stable free radical inhibitors. The former mainly include: hydroquinone, p-benzoquinone, phenothiazine, β-phenylnaphthylamine, p-tert-butyl-phthalate Diphenol, methylene blue, tris(N-nitroso-N-phenylhydroxylamine) aluminum salt, cuprous chloride, ferric chloride and other inorganic substances and sulfur can also be used as polymerization inhibitors to stabilize free radical polymerization inhibitors There are mainly 1,1-diphenyl-2-picrylhydrazine (DPPH), 2,2,6,6-tetramethylpiperidine nitroxide radical (TMP), hydroquinone, allyl acetate, p- Hydroxyanisole (MEHQ), nitroxide radical piperidinol, phosphorous acid (2,2,6,6-tetramethylpiperidine nitroxide radical) mixed ester, 4-hydroxy-2,2,6, 6-Tetramethylpiperidine-1-oxyl radical (TMHPHA), 8% tris(N-nitroso-N-phenylhydroxylamine) aluminum salt: 92% 2-phenolethoxyacrylate, 4 % Tris(N-nitroso-N-phenylhydroxylamine) aluminum salt, 96% ethoxylated mono-oil triacrylate, hydroquinone methyl ether, copper salt of polymerization inhibitor, o-methylhydroquinone, 2 ,6-di-tert-butyl cresol, dimethyl hydroquinone, p-tert-butyl catechol (TBC), catechol, p-methoxyphenol, 2.6-di-tert-butyl p-cresol, 2.5-di tert-butylhydroquinone, p-benzoquinone, methylhydroquinone, 1.4-naphthoquinone, phenothiazine, tert-butylhydroquinone (TBHQ), o-sec-butyl-4,6 dinitrophenol ( DNBP), ethylene glycol monopropyl ether, alkylbenzenesulfonic acid amine salt, p-tert-butylcatechol, methyl methacrylate (MMA), 2,4,6-trinitrophenol (TNP), 2 ,4-Dimethyl-6-tert-butylphenol (TBX), N,N-diethylhydroxylamine (DEHA), p-tert-butylcatechol, 2,5-di-tert-butylhydroquinone, ortho Methyl-p-phthalenedi-o-methyl-p-benzoquinone, 3-tert-butyl-4-hydroxyanisole (BHA), 2,6-dinitro-p-cresol (DNPC), polyvinyl acetal, nitrogen Oxygen free radical piperidinol, 4,6-dinitro-o-sec-butylphenol, dimethyl succinyl succinate (DMSS), propynyl alcohol.

触变剂加入树脂中,能使树脂胶液在静止时有较高的稠度,在外力作用下又变成低稠度流体的物质。有机膨润土丁腈橡胶(NBR)、蒙脱石(Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2})、膨润土[(Nax(H2O)4(Al2-xMg0.83)Si4O10)(OH)2]、硅藻土(无定形的SiO2组成,并含有少量Fe2O3、CaO、MgO、Al2O3及有机杂质)、石棉、硅灰石(CaSiO3)、白云母(KAl2(AlSi3O10)(OH)2)、金云母(KMg3(AlSi3O10)(F,OH)2)、镁硅白云母[K2((Fe2+Mg)(Fe3+Al)3(Si7AlO20)(OH)4)]、蒙脱石[Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2}]、膨润土[Nax(H2O)4(Al2-xMg0.83)(Si4O10)(OH)2]、氢化蓖麻油、气相法二氧化硅、金属皂(硬脂酸铅、钡、镉、钙、锌、镁、铝、稀土)。在水性体系中则用羟乙基纤维素等纤维素衍生物,聚乙烯醇、聚丙烯酸、聚环氧乙烷、聚甲基丙烯酸、脲醛树脂、三聚氰胺甲醛树脂、甲阶段酚醛树脂、酚醛树脂水溶性树脂为增稠剂。The thixotropic agent is added to the resin, which can make the resin glue have a higher consistency when it is still, and become a low-viscosity fluid under the action of an external force. Organobentonite nitrile rubber (NBR), montmorillonite (Na x (H 2 O) 4 {(Al 2-x Mg 0.33 )[Si 4 O 10 ](OH) 2 }), bentonite [(Na x (H 2 O) 4 (Al 2-x Mg 0.83 )Si 4 O 10 )(OH) 2 ], diatomaceous earth (amorphous SiO 2 composition, and contains a small amount of Fe 2 O 3 , CaO, MgO, Al 2 O 3 and organic impurities), asbestos, wollastonite (CaSiO 3 ), muscovite (KAl 2 (AlSi 3 O 10 )(OH) 2 ), phlogopite (KMg 3 (AlSi 3 O 10 )(F,OH) 2 ) , magnesium silicate muscovite [K 2 ((Fe 2 +Mg)(Fe 3 +Al) 3 (Si 7 AlO 20 )(OH) 4 )], montmorillonite [Na x (H 2 O) 4 {(Al 2-x Mg 0.33 )[Si 4 O 10 ](OH) 2 }], bentonite [Na x (H 2 O) 4 (Al 2-x Mg 0.83 )(Si 4 O 10 )(OH) 2 ], hydrogenation Castor oil, fumed silica, metal soaps (lead stearate, barium, cadmium, calcium, zinc, magnesium, aluminum, rare earths). In the water-based system, cellulose derivatives such as hydroxyethyl cellulose, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polymethacrylic acid, urea-formaldehyde resin, melamine-formaldehyde resin, resol phenolic resin, and phenolic resin are used to dissolve water. Resins are thickeners.

填充剂的作用是部分代替粘结剂,减少粘结剂的耗用量,以达到填充、补强、减磨和降低成本的效果。填充剂要求粒子细而匀,能均匀地分散于浆液中,对粘结剂和其他组分结合性良好。填充剂的用量应适当,否则也会影响浆膜质量。包括无机矿物膨润土丁腈橡胶(NBR)、硅铝酸钾钠(霞石)、碳酸钙、含水的矽酸镁[Mg3[Si4O10](OH)2]、硅灰石(CaSiO3)、白云母[KAl2(AlSi3O10)(OH)2]、金云母[KMg3(AlSi3O10)(FOH)2]、镁硅白云母[K2((Fe2+Mg)(Fe3+Al)3(Si7AlO20)(OH)4)]、蒙脱石[Nax(H2O)4{(Al2-xMg0.33)[Si4O10](OH)2}]、膨润土[Nax(H2O)4(Al2-xMg0.83)(Si4O10)(OH)2]、高岭土、赤泥(Al1-xOx)、硫酸钙、丙烯酸酯高聚物、聚丙烯酸丁酯、聚氨酯。The role of the filler is to partially replace the binder and reduce the consumption of the binder to achieve the effects of filling, reinforcement, wear reduction and cost reduction. The filler requires fine and uniform particles, can be uniformly dispersed in the slurry, and has good binding properties to the binder and other components. The amount of filler should be appropriate, otherwise it will affect the quality of the serous film. Including inorganic mineral bentonite nitrile rubber (NBR), potassium sodium aluminosilicate (nepheline), calcium carbonate, hydrous magnesium silicate [Mg 3 [Si 4 O 10 ](OH) 2 ], wollastonite (CaSiO 3 ), muscovite [KAl 2 (AlSi 3 O 10 ) (OH) 2 ], phlogopite [KMg 3 (AlSi 3 O 10 ) (FOH) 2 ], magnesium silicon muscovite [K 2 ((Fe 2 +Mg) (Fe 3 +Al) 3 (Si 7 AlO 20 )(OH) 4 )], montmorillonite [Na x (H 2 O) 4 {(Al 2-x Mg 0.33 )[Si 4 O 10 ](OH) 2 }], bentonite [Na x (H 2 O) 4 (Al 2-x Mg 0.83 )(Si 4 O 10 )(OH) 2 ], kaolin, red mud (Al 1-x O x ), calcium sulfate, Acrylate polymer, polybutylacrylate, polyurethane.

分散剂促使物料颗粒均匀分散于介质中,形成稳定悬浮体的试剂。分散剂一般分为无机分散剂和有机分散剂两大类。常用的无机分散剂有硅酸盐类(例如水玻璃)和碱金属膦酸盐类(氨基三甲叉膦酸四钠、氨基三甲叉膦酸五钠、氨基三甲叉膦酸钾、羟基乙叉二膦酸钠、羟基乙叉二膦酸二钠、羟基乙叉二膦酸四钠、羟基乙叉二膦酸钾、乙二胺四甲叉膦酸五钠、二乙烯三胺五甲叉膦酸五钠、二乙烯三胺五亚甲基膦酸七钠、二乙烯三胺五甲叉膦酸钠、2-膦酸丁烷-1,2,4-三羧酸四钠、己二胺四甲叉膦酸钾盐、双1,6亚己基三胺五甲叉膦酸钠、三聚膦酸钠、六偏磷酸钠和焦磷酸钠等)。有机分散剂包括三乙基己基膦酸、氨基三甲叉膦酸、羟基乙叉二膦酸(HEDP)、乙二胺四甲叉膦酸钠(EDTMPS)、乙二胺四甲叉膦酸(EDTMPA)、二乙烯三胺五甲叉膦酸(DTPMP)、2-膦酸丁烷-1,2,4-三羧酸(PBTCA)、多元醇磷酸酯(PAPE)、2-羟基膦酰基乙酸(HPAA)、己二胺四甲叉膦酸(HDTMPA)、多氨基多醚基甲叉膦酸(PAPEMP)、双1,6亚己基三胺五甲叉膦酸(BHMTPMPA)、十二烷基硫酸钠、聚丙烯酸(PAA)、聚丙烯酸钠(PAAS)、水解聚马来酸酐(HPMA)、马来酸-丙烯酸共聚物(MA-AA)、丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物(AA/AMPS)、丙烯酸-丙烯酸羟丙酯共聚物、丙烯酸-丙烯酸酯-膦酸-磺酸盐四元共聚物、丙烯酸-丙烯酸酯-磺酸盐三元共聚物、膦酰基羧酸共聚物(POCA)、聚丙烯酸盐、羧酸盐-磺酸盐-非离子三元共聚物、聚环氧琥珀酸钠(PESA)、聚天冬氨酸钠(PASP)、基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯等。Dispersant is a reagent that promotes the uniform dispersion of material particles in the medium to form a stable suspension. Dispersants are generally divided into two categories: inorganic dispersants and organic dispersants. Commonly used inorganic dispersants include silicates (such as water glass) and alkali metal phosphonates (tetrasodium aminotrimethylene phosphonate, pentasodium aminotrimethylene phosphonate, potassium aminotrimethylene phosphonate, Sodium phosphonate, disodium hydroxyethylidene diphosphonate, tetrasodium hydroxyethylidene diphosphonate, potassium hydroxyethylidene diphosphonate, pentasodium ethylenediaminetetramethylenephosphonate, diethylenetriaminepentamethylenephosphonate Pentasodium, heptasodium diethylenetriaminepentamethylenephosphonate, sodium diethylenetriaminepentamethylenephosphonate, tetrasodium 2-butane-1,2,4-tricarboxylate, tetrasodium hexamethylenediamine Potassium methylene phosphonate, sodium bis-1,6 hexamethylene triamine penta-methylene phosphonate, sodium tripolyphosphonate, sodium hexametaphosphate and sodium pyrophosphate, etc.). Organic dispersants include triethylhexylphosphonic acid, aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid (HEDP), sodium ethylenediaminetetramethylenephosphonate (EDTMPS), ethylenediaminetetramethylenephosphonic acid (EDTMPA) ), diethylenetriaminepentamethylenephosphonic acid (DTPMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA), polyol phosphate (PAPE), 2-hydroxyphosphonoacetic acid ( HPAA), hexamethylenediaminetetramethylenephosphonic acid (HDTMPA), polyaminopolyether methylenephosphonic acid (PAPEMP), bis-1,6-hexamethylenetriaminepentamethylenephosphonic acid (BHMTPMPA), lauryl sulfate Sodium, polyacrylic acid (PAA), sodium polyacrylate (PAAS), hydrolyzed polymaleic anhydride (HPMA), maleic acid-acrylic acid copolymer (MA-AA), acrylic acid-2-acrylamide-2-methylpropanesulfonate Acid copolymer (AA/AMPS), acrylic acid-hydroxypropyl acrylate copolymer, acrylic acid-acrylate-phosphonic acid-sulfonate tetrapolymer, acrylic acid-acrylate-sulfonate terpolymer, phosphonocarboxylate Acid copolymer (POCA), polyacrylate, carboxylate-sulfonate-nonionic terpolymer, polyepoxysuccinate sodium (PESA), polyaspartate sodium (PASP), amyl amyl alcohol, Cellulose derivatives, polyacrylamide, gull gum, fatty acid polyethylene glycol esters, etc.

抗氧剂以抑制聚合物树脂热氧化降解为主要功能的助剂,属于抗氧化试剂的范畴。抗氧剂是塑料稳定化助剂最主要的类型,几乎所有的聚合物树脂都涉及到抗氧剂的应用。按照作用机理,传统的抗氧剂体系一般包括主抗氧剂、辅助抗氧剂和重金属离子钝化剂等。主抗氧剂以捕获聚合物过氧自由基为主要功能,又有“过氧自由基捕获剂”和“链终止型抗氧剂”之称,涉及芳胺类化合物和受阻酚类化合物两大系列产品。芳香胺类抗氧剂有:二苯胺、对苯二胺、N,N-双-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]己二胺、二氢喹啉;受阻酚类抗氧剂有:2,5-二特丁基对苯二酚、2,6-二叔丁基-4-甲基苯酚、叔丁基对苯二酚、2,5-二特丁基对苯二酚(DBHQ)、2,6-三级丁基-4-甲基苯酚、双(3,5-三级丁基-4-羟基苯基)硫醚、四[β-(3,5-三级丁基-4-羟基苯基)丙酸]季戊四醇酯;亚磷酸三苯酯(TPPi)、亚磷酸酯三(2,4-二特丁基苯基)酯、季戊四醇双亚磷酸酯二(2,4-二特丁基苯基)酯、多烷基双酚A亚磷酸酯的双聚体和三聚体的复合物、3,5-二叔丁基-4-羟基苄基二乙基膦酸酯、亚磷酸三(2,4-二叔丁基苯基)酯、β-(4-羟基苯基-3,5-二叔丁基)丙酸正十八碳醇酯、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苯甲基)苯。辅助抗氧剂具有分解聚合物过氧化合物的作用,也称“过氧化物分解剂”,包括硫代二羧酸酯类和亚磷酸酯化合物,通常和主抗氧剂配合使用。双十二碳醇酯、双十四碳醇酯、硫代二丙酸双十八酯(DSTP)、硫代二丙酸双酯、双十八碳醇酯、硫代二丙酸双月桂酯、三辛酯、三癸酯、三(十二碳醇)酯和三(十六碳醇)酯、3,6,9-三氧杂癸烷-1,11-二醇-双-正十二烷巯基丙酸酯、磷酸三苯酯TPP、亚磷酸三壬基苯酯、亚磷酸辛基二苯基酯。Antioxidants are additives whose main function is to inhibit the thermal oxidation degradation of polymer resins, and belong to the category of antioxidant agents. Antioxidants are the most important type of plastic stabilization additives, and almost all polymer resins involve the application of antioxidants. According to the mechanism of action, the traditional antioxidant system generally includes primary antioxidants, auxiliary antioxidants and heavy metal ion deactivators. The main function of the primary antioxidant is to capture polymer peroxyl radicals, and it is also known as "peroxyl radical scavenger" and "chain-terminating antioxidant". It involves two major types of aromatic amine compounds and hindered phenolic compounds. series of products. Aromatic amine antioxidants include: diphenylamine, p-phenylenediamine, N,N-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hexamethylenediamine, dihydro Quinoline; hindered phenolic antioxidants include: 2,5-di-tert-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol, tert-butyl hydroquinone, 2,5 -Di-tert-butyl hydroquinone (DBHQ), 2,6-tertiary butyl-4-methylphenol, bis(3,5-tertiary butyl-4-hydroxyphenyl)sulfide, tetrakis[ β-(3,5-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol; triphenyl phosphite (TPPi), tris(2,4-di-tert-butylphenyl) phosphite , Pentaerythritol bisphosphite bis (2,4-di-tert-butylphenyl) ester, complexes of dimers and trimers of polyalkylbisphenol A phosphite, 3,5-di-tert-butyl -4-Hydroxybenzyldiethylphosphonate, tris(2,4-di-tert-butylphenyl)phosphite, β-(4-hydroxyphenyl-3,5-di-tert-butyl)propionic acid n-octadecyl alcohol ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene. Auxiliary antioxidants have the function of decomposing polymer peroxygen compounds, also known as "peroxide decomposers", including thiodicarboxylates and phosphite compounds, and are usually used in conjunction with primary antioxidants. Dilauryl alcohol ester, ditetradecyl alcohol ester, dioctadecyl thiodipropionate (DSTP), diester thiodipropionate, dioctadecyl alcohol ester, dilauryl thiodipropionate , trioctyl, tridecyl, tri(dodecyl) and tri(hexadecanyl) esters, 3,6,9-trioxadecane-1,11-diol-bis-n-deca Dialkylmercaptopropionate, Triphenyl Phosphate TPP, Trinonylphenyl Phosphite, Octyldiphenyl Phosphite.

重金属离子钝化剂,俗称“抗铜剂”,能够络合过渡金属离子,防止其催化聚合物树脂的氧化降解反应,典型的结构如酰肼类化合物等。最近几年,随着聚合物抗氧理论研究的深入,抗氧剂的分类也发生了一定的变化,最突出的特征是引入了“碳自由基捕获剂”的概念。这种自由基捕获剂有别于传统意义上的主抗氧剂,它们能够捕获聚合物烷基自由基,相当于在传统抗氧体系中增设了一道防线。此类稳定化助剂主要包括2-乙基苯并呋喃酮、2-甲基苯并呋喃酮、二氢苯并呋喃酮、苯并呋喃酮、二苯并呋喃酮、3-芳基-苯并呋喃-2-酮、3-芳基苯并呋喃酮、2-芳基二氢苯并呋喃酮、2-芳基苯并呋喃酮、5-氰基-1-(4-氟苯基)-1,3-二氢异苯并呋喃酮、5-取代1-(4-氟苯基)-1,3-二氢异苯并呋喃酮、2,3-二羟基-2,2-二甲基-7-苯并呋喃酚、3-(2-酰氧基乙氧基苯基)苯并呋喃-2-酮、异苯并呋喃酮、5-[(咪唑并[4,5-b]吡啶-3-基)甲基]苯并呋喃酮、1,2,3,4-四氢-苯并呋喃酮、2,3-二氢-2-甲基-2-烷基苯并呋喃酮、4-乙氧基双酚-A-二丙烯酸酯、(2-10)-乙氧化双酚-A-二甲基丙烯酸酯、2-[1-(2-羟基-3,5-二特戊基苯基)-乙基]-4,6-二特戊基苯基丙烯酸酯、双酚-A-丙三醇双甲基丙烯酸酯、双酚-A-二甲基丙烯酸酯、4-乙氧基双酚-A-二甲基丙烯酸酯、N,N-二苄基羟胺、N-乙基-N-羟基乙胺、N,N-二乙基羟胺、异佛尔酮二胺丙烯酰胺硫酸羟胺、异丙基羟胺、盐酸羟胺、氯化羟铵、氢氯羟胺、N-甲基-羟胺、醋羟胺酸、N-羟基乙酰胺。Heavy metal ion deactivators, commonly known as "anti-copper agents", can complex transition metal ions and prevent them from catalyzing the oxidative degradation reaction of polymer resins. Typical structures are hydrazide compounds, etc. In recent years, with the in-depth study of polymer antioxidant theory, the classification of antioxidants has also undergone certain changes. The most prominent feature is the introduction of the concept of "carbon free radical scavenger". This kind of free radical scavenger is different from the main antioxidant in the traditional sense. They can capture polymer alkyl free radicals, which is equivalent to adding a line of defense to the traditional antioxidant system. Such stabilizers mainly include 2-ethylbenzofuranone, 2-methylbenzofuranone, dihydrobenzofuranone, benzofuranone, dibenzofuranone, 3-aryl-benzene Furan-2-one, 3-arylbenzofuranone, 2-aryldihydrobenzofuranone, 2-arylbenzofuranone, 5-cyano-1-(4-fluorophenyl) -1,3-dihydroisobenzofuranone, 5-substituted 1-(4-fluorophenyl)-1,3-dihydroisobenzofuranone, 2,3-dihydroxy-2,2-di Methyl-7-benzofuranol, 3-(2-acyloxyethoxyphenyl)benzofuran-2-one, isobenzofuranone, 5-[(imidazo[4,5-b] Pyridin-3-yl)methyl]benzofuranone, 1,2,3,4-tetrahydro-benzofuranone, 2,3-dihydro-2-methyl-2-alkylbenzofuranone , 4-ethoxybisphenol-A-diacrylate, (2-10)-ethoxylated bisphenol-A-dimethacrylate, 2-[1-(2-hydroxy-3,5-dimethacrylate Pentylphenyl)-ethyl]-4,6-di-t-pentylphenyl acrylate, bisphenol-A-glycerol dimethacrylate, bisphenol-A-dimethacrylate, 4- Ethoxylated bisphenol-A-dimethacrylate, N,N-dibenzylhydroxylamine, N-ethyl-N-hydroxyethylamine, N,N-diethylhydroxylamine, isophoronediaminepropene Amides Hydroxylamine Sulfate, Isopropyl Hydroxylamine, Hydroxylamine Hydrochloride, Hydroxylammonium Chloride, Hydroxylamine Hydroxylamine, N-Methyl-Hydroxylamine, Acetohydroxylamine, N-Glyoxetamide.

加工改性剂旨在改善塑化性能、提高树脂熔体黏弹性和促进树脂熔融流动的改性助剂,此类助剂以丙烯酸酯类共聚物(ACR)为主。Processing modifiers are modified additives aimed at improving plasticizing properties, improving resin melt viscoelasticity and promoting resin melt flow. Such additives are mainly acrylate copolymers (ACR).

抗冲击改性剂提高硬质聚合物制品抗冲击性能的助剂。主要包括氯化聚乙烯(CPE)、丙烯酸酯共聚物(ACR)、甲基丙烯酸酯-二烯-乙烯共聚物(MBS)、乙烯-烯基醋酸酯共聚物(EVA)和丙烯腈-二烯-乙烯共聚物(ABS)等。聚丙烯增韧改性中使用的三元乙丙橡胶(EPDM)亦属橡胶增韧的范围。Impact modifier is an additive to improve the impact resistance of rigid polymer products. Mainly including chlorinated polyethylene (CPE), acrylate copolymer (ACR), methacrylate-diene-ethylene copolymer (MBS), ethylene-vinyl acetate copolymer (EVA) and acrylonitrile-diene - Ethylene copolymer (ABS), etc. The ethylene-propylene-diene rubber (EPDM) used in the toughening modification of polypropylene also belongs to the scope of rubber toughening.

抗静电剂的功能在于降低聚合物制品的表面电阻,消除静电积累可能导致的静电危害,主要包括为阳离子表面活性剂和阴离子表面活性剂。阳离子表面活性剂有:烷基磷酸酯二乙醇胺盐、十八烷基二甲基苄基氯化铵、硬脂酰三甲基氯化铵、硬脂酰胺、硬脂酰二甲基戊基氯化铵、N,N-双(2-羟乙基)-N-(3’-十二烷氧基-2’-羟基丙基)甲铵硫酸甲酯盐、三羟乙基甲基季铵硫酸甲酯盐、硬脂酰胺丙基二甲基-β-羟乙基铵二氢磷酸盐、N,N-十六烷基乙基吗啉硫酸乙酯盐、(月桂酰胺丙基三甲基铵)硫酸甲酯盐二溴化N,N-二(十八烷基二甲基)-3-氧杂-1,5-戊二铵、苯乙烯聚合物型季铵盐、棕榈酸酯季铵盐、烷基酚聚氧乙烯基季铵盐、双烷基季铵盐、聚丙烯酰胺季铵盐、十八烷基二甲基羟乙基季铵硝酸盐、聚苯乙烯磺酸铵盐、丙基二甲基-β-羟乙基硝酸盐,(3-月桂酰胺丙基)三甲基铵硫酸甲酯盐、2,2′-次氮基双乙醇与α-三癸基-ω-羟基聚(氧-1,2-乙二基)磷酸酯的聚合物、聚乙二醇十三烷基醚磷酸酯、二乙醇胺盐、油酸二乙醇胺盐、油酸三乙醇胺盐、乙氧化胺、N,N-二羟乙基十八胺、N,N-二羟乙基对甲苯胺、烷基酚聚氧乙烯基季铵盐、羟乙基季铵盐、氧杂含氟季铵盐;阴离子表面活性剂有:脂肪醇醚磷酸酯、酚醚磷酸酯(TXP-4)、酚醚磷酸酯(TXP-10)、异十三醇磷酸酯、月桂基磷酸酯(MA24P)、脂肪醇醚磷酸酯钾(MOA-3PK)、酚醚磷酸酯钾盐(NP-4PK)、酚醚磷酸酯钾盐(NP-10PK)、异十三醇醚磷酸酯钾盐、月桂基磷酸酯钾盐(MA24PK)、脂肪醇磷酸酯钾盐、烯丙基磺酸钠;非离子表面活性剂:烷基胺与环氧乙烷的缩合物、烷醇酰胺、脂肪醇聚氧乙烯醚、脂肪酸聚氧乙烯醚、双(β-羟乙基)椰油胺、双(β-羟乙基)硬脂胺、双(β-羟乙基)牛油胺、六甲基磷酰三胺、全氟烷基乙醇聚氧乙烯醚。The function of antistatic agents is to reduce the surface resistance of polymer products and eliminate the electrostatic hazards that may be caused by static electricity accumulation, mainly including cationic surfactants and anionic surfactants. Cationic surfactants are: alkyl phosphate diethanolamine salt, octadecyl dimethyl benzyl ammonium chloride, stearyl trimethyl ammonium chloride, stearyl amide, stearyl dimethyl pentyl chloride Ammonium chloride, N,N-bis(2-hydroxyethyl)-N-(3'-dodecyloxy-2'-hydroxypropyl)methylammonium methyl sulfate, trihydroxyethylmethyl quaternary ammonium Methyl sulfate, stearamidopropyl dimethyl-β-hydroxyethyl ammonium dihydrogen phosphate, N,N-hexadecyl ethyl morpholine ethyl sulfate, (lauryl amidopropyl trimethyl Ammonium) methyl sulfate dibromide N,N-bis(octadecyldimethyl)-3-oxa-1,5-pentammonium dibromide, styrene polymer type quaternary ammonium salt, palmitate quaternary Ammonium salt, alkylphenol polyoxyethylene quaternary ammonium salt, dialkyl quaternary ammonium salt, polyacrylamide quaternary ammonium salt, octadecyldimethylhydroxyethyl quaternary ammonium nitrate, polystyrene sulfonate ammonium salt , Propyldimethyl-β-Hydroxyethyl Nitrate, (3-Lauramidopropyl) Trimethylammonium Methyl Sulfate, 2,2′-Nitrilobisethyl Ethanol and α-Tridecyl-ω -Polymer of hydroxy poly(oxy-1,2-ethylenediyl)phosphate, polyethylene glycol tridecyl ether phosphate, diethanolamine salt, oleic acid diethanolamine salt, oleic acid triethanolamine salt, ethoxylated Amine, N,N-dihydroxyethyl octadecylamine, N,N-dihydroxyethyl p-toluidine, alkylphenol polyoxyethylene quaternary ammonium salt, hydroxyethyl quaternary ammonium salt, oxafluorine-containing quaternary ammonium Salt; anionic surfactants are: fatty alcohol ether phosphate, phenol ether phosphate (TXP-4), phenol ether phosphate (TXP-10), isotridecanyl phosphate, lauryl phosphate (MA24P), fat Potassium alcohol ether phosphate (MOA-3PK), potassium phenol ether phosphate (NP-4PK), potassium phenol ether phosphate (NP-10PK), potassium isotridecanthyl phosphate, potassium lauryl phosphate Salt (MA24PK), potassium salt of fatty alcohol phosphate, sodium allyl sulfonate; nonionic surfactants: condensation products of alkylamine and ethylene oxide, alkanolamide, fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene Oxyethylene ether, bis(β-hydroxyethyl)cocamine, bis(β-hydroxyethyl)stearylamine, bis(β-hydroxyethyl)tallowamine, hexamethylphosphoric triamide, perfluorinated Alkyl alcohol polyoxyethylene ether.

阴阳两性型表面活性剂包括:十二烷基-二甲基季铵乙内盐、十二烷基二甲基季铵乙内盐、烷基二羟乙基铵乙内盐、N-烷基氨基酸盐、环氧三聚体磺酸内盐、羧基甜菜碱、十三烷基二甲基(2-亚硫酸)乙基铵乙内盐、N-十二烷基丙氨酸、3-氯丙胺盐酸盐、N-叔丁氧羰基-D-3-(2-萘基)-丙氨酸、N-叔丁氧基羰基-D-2-萘丙氨酸、叔丁氧羰基-D-2-萘丙氨酸、叔丁氧羰基-D-3-(2-萘基)-丙氨酸、N-叔丁氧羰基-L-2-三氟甲基苯丙氨酸、草甘膦异丙胺盐。Amphoteric surfactants include: dodecyl-dimethyl quaternary ammonium betaine, dodecyl dimethyl quaternary ammonium betaine, alkyl dihydroxyethyl ammonium betaine, N-alkyl Amino acid salt, epoxy trimer sulfonic acid internal salt, carboxybetaine, tridecyldimethyl (2-sulfite) ethylammonium hydantoin, N-dodecylalanine, 3-chloro Propylamine hydrochloride, N-tert-butoxycarbonyl-D-3-(2-naphthyl)-alanine, N-tert-butoxycarbonyl-D-2-naphthylalanine, tert-butoxycarbonyl-D -2-Naphthylalanine, tert-butoxycarbonyl-D-3-(2-naphthyl)-alanine, N-tert-butoxycarbonyl-L-2-trifluoromethylphenylalanine, glyphosate Phosphine isopropylamine salt.

高分子型抗静电剂包括:聚环氧乙烷(PEO)、聚醚酯酰亚胺、聚乙烯乙二醇甲基丙烯酸共聚体、聚醚酯酰胺(PEEA)、聚醚酯乙酰胺(PEAI)、聚氧化乙烯、环氧丙烷共聚物(PEO-ECH)、聚乙二醇甲基丙烯酸酯(PEGMA)、甲基丙烯酸(MAA)、甲基丙烯酸十八烷基酯(SMA)+聚乙二醇甲基丙烯酸酯(PEGMA)组成的两亲性共聚物。Polymer antistatic agents include: polyethylene oxide (PEO), polyether ester imide, polyethylene glycol methacrylic acid copolymer, polyether ester amide (PEEA), polyether ester acetamide (PEAI ), polyethylene oxide, propylene oxide copolymer (PEO-ECH), polyethylene glycol methacrylate (PEGMA), methacrylic acid (MAA), octadecyl methacrylate (SMA) + polyethylene Amphiphilic copolymer composed of glycol methacrylate (PEGMA).

阻燃剂中无机阻燃剂包括三氧化二锑、钼酸锌、氧化锌、氧化铁、氧化锡、氢氧化铝、氢氧化镁、氧化锑、硼酸锌和赤磷;有机阻燃剂包括十溴二苯醚、三(2,3-二溴丙基)磷酸酯、六溴环十二烷、聚2,6-二溴苯醚、氯化石蜡、多磷酸酯、红磷、双(四溴邻苯二甲酰亚胺)乙烷、二溴苯乙烯均聚物、三聚氰胺、三聚氰酸盐、异癸基二苯基磷酸酯、乙基己基二苯基磷酸酯、磷酸三异丙苯酯、双(2氯乙基)乙烯基膦酸酯、乙撑双[三(2氰乙基)溴化磷盐]、N,N双(2羟乙基)氨甲基膦酸二乙酯、聚苯基膦酸二苯砜酯、聚苯基膦酸二苯偶氮酯、聚苯基膦酸双酚A酯。Inorganic flame retardants in flame retardants include antimony trioxide, zinc molybdate, zinc oxide, iron oxide, tin oxide, aluminum hydroxide, magnesium hydroxide, antimony oxide, zinc borate and red phosphorus; organic flame retardants include ten Brominated diphenyl ether, tris(2,3-dibromopropyl) phosphate, hexabromocyclododecane, poly 2,6-dibromophenyl ether, chlorinated paraffin, polyphosphate, red phosphorus, bis(tetrafluoroethylene bromophthalimide) ethane, dibromostyrene homopolymer, melamine, cyanurate, isodecyl diphenyl phosphate, ethylhexyl diphenyl phosphate, triisopropyl phosphate Phenyl ester, bis(2 chloroethyl)vinyl phosphonate, ethylene bis[tris(2 cyanoethyl)phosphonium bromide], N,N bis(2 hydroxyethyl)aminomethylphosphonic acid diethyl Ester, polyphenylsulfone diphenylphosphonate, diphenylazo polyphenylphosphonate, bisphenol A polyphenylphosphonate.

防霉剂又称微生物抑制剂,是一类抑制霉菌等微生物生长,防止聚合物树脂被微生物侵蚀而降解的稳定化助剂。绝大多数聚合物材料对霉菌并不敏感,但由于其制品在加工中添加了增塑剂、润滑剂、脂肪酸皂类等可以滋生霉菌类的物质而具有霉菌感受性。塑料用防霉剂所包含的化学物质很多,比较常见的品种包括有机金属化合物(如有机汞、有机锡、有机铜、有机砷等)、含氮有机化合物、含硫有机化合物、含卤有机化合物和酚类衍生物等。其中包括苯酚、五氯酚、油酸苯基汞、8-羟基喹啉铜、氯化三乙或三丁基锡、硫酸铜、氯化汞、氟化钠。Antifungal agent, also known as microbial inhibitor, is a kind of stabilizing agent that inhibits the growth of microorganisms such as mold and prevents polymer resins from being eroded by microorganisms and degraded. The vast majority of polymer materials are not sensitive to mold, but because of the addition of plasticizers, lubricants, fatty acid soaps and other substances that can breed mold in their products, they have mold susceptibility. Antifungal agents for plastics contain many chemical substances, and the more common ones include organic metal compounds (such as organic mercury, organic tin, organic copper, organic arsenic, etc.), nitrogen-containing organic compounds, sulfur-containing organic compounds, and halogen-containing organic compounds. and phenolic derivatives, etc. These include phenol, pentachlorophenol, phenylmercury oleate, copper 8-hydroxyquinolate, triethyl or tributyltin chloride, copper sulfate, mercuric chloride, sodium fluoride.

增感剂为对二甲氨基苯甲酰胺;促进剂中氨丙基倍半硅氧烷与低分子聚酰胺质量比为3:1。The sensitizer is p-dimethylaminobenzamide; the mass ratio of aminopropyl silsesquioxane to low molecular weight polyamide in the accelerator is 3:1.

阳离子型光固化体系主要利用芳香族重氮盐、芳香族碘鎓盐、芳香族锍盐在紫外线照射下光解产生质子酸,质子酸再引发单体进行阳离子聚合。与自由基固化体系相比,它具有固化收缩率小、不受各种氧的阻聚作用以及若没有亲核杂质存在,一旦引发,聚合就会长期继续下去等优点。但是,光引发剂在光照射时释放出的质子酸,对胶结基体会产生腐蚀作用。理论上,凡能进行阳离子聚合的单体都可以用于阳离子固化,但是,目前最常用的是各种环氧树脂或改性环氧树脂。各种活性环氧树脂稀释剂以及各种环醚、环内酯、乙烯基醚单体等都可以作为光固化树脂的稀释剂,阳离子光引发剂有二芳基碘鎓盐、三芳基碘鎓盐、三芳基硫鎓盐、三芳基硒鎓盐等。目前,围绕着这一体系的研究越来越多,例如有报导利用含氟以及不含氟的混合树脂在上述阳离子引发剂引发,制得了低收缩率且折射率可调的精密胶粘剂;在光盘制作中,利用阳离子引发的环氧树脂制得的胶粘剂在85℃、相对湿度为95%的实验条件下,96h无侵蚀现象发生;在中空装置的组装时,利用锍盐引发的脂肪族和双酚D-型混合环氧树脂,可以制得低线膨胀系数且具有良好防潮性的胶粘剂。The cationic photocuring system mainly uses aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts to photolyze under ultraviolet light to generate protonic acids, which then initiate cationic polymerization of monomers. Compared with the free radical curing system, it has the advantages of small curing shrinkage, no inhibition of various oxygen, and if there is no nucleophilic impurity, once initiated, the polymerization will continue for a long time. However, the protonic acid released by the photoinitiator under light irradiation will corrode the cemented matrix. Theoretically, any monomer that can undergo cationic polymerization can be used for cationic curing, but at present, various epoxy resins or modified epoxy resins are most commonly used. Various active epoxy resin diluents and various cyclic ethers, cyclic lactones, vinyl ether monomers, etc. can be used as diluents for photocurable resins. Cationic photoinitiators include diaryliodonium salts and triaryliodonium salts. salt, triarylsulfonium salt, triarylselenium salt, etc. At present, there are more and more researches on this system. For example, it is reported that the use of fluorine-containing and fluorine-free hybrid resins is initiated by the above-mentioned cationic initiator, and a precision adhesive with low shrinkage and adjustable refractive index is prepared; In the production, the adhesive prepared by using cationic-initiated epoxy resin did not corrode for 96 hours under the experimental conditions of 85 ° C and 95% relative humidity; when assembling the hollow device, the aliphatic and bis Phenolic D-type hybrid epoxy resin, which can produce adhesives with low linear expansion coefficient and good moisture resistance.

2,4,6-三甲基苯甲酰基二苯基氧化膦(TPO),芳茂铁盐、有机铝络合物/硅烷体系、二烷基苯酸甲基硫翁盐,三芳基硫鎓六氟磷酸盐阳离子光引发剂-桐油改性酚醛环氧树脂(TMPE)和E-44环氧树脂复配体系的阳离子光固化反应.通过凝胶率的测定研究了各种条件对光固化速度的影响,并利用红外光谱分析了该反应体系光固化反应前后涂膜结构。结果表明,光引发剂的种类和浓度可以有效地改变光固化速度,Omnicat550的引发活性优于Omnicat432且与其浓度成比例;蒽、BPO等光敏化刑对体系有一定的增感作用,而吩噻嗪作用不明显;不同种类的环氧及乙烯基醚类活性稀释剂对光固化速度有较大影响;随着树脂配比中环氧基团浓度的增加光固化速度增大;该体系表现出“后固化”现象。2,4,6-Trimethylbenzoyldiphenylphosphine oxide (TPO), ferrocene salt, organoaluminum complex/silane system, methylsulfonium dialkylbenzoate, triarylsulfonium Cationic photocuring reaction of hexafluorophosphate cationic photoinitiator-tung oil modified novolak epoxy resin (TMPE) and E-44 epoxy resin compound system. The effect of various conditions on photocuring speed was studied by measuring the gel ratio , and analyzed the structure of the coating film before and after the photocuring reaction of the reaction system by infrared spectroscopy. The results show that the type and concentration of photoinitiator can effectively change the photocuring speed. The initiation activity of Omnicat550 is better than that of Omnicat432 and is proportional to its concentration; The effect of oxazine is not obvious; different types of epoxy and vinyl ether reactive diluents have a great influence on the photocuring speed; with the increase of the epoxy group concentration in the resin ratio, the photocuring speed increases; the system shows "Post-cure" phenomenon.

由于光引发阳离子聚合体系具有光引发不够理想、固化速度慢、成本高等缺陷,限制了它在工业上的推广,有人将环氧树脂的阳离子聚合和丙烯酸酯的自由基聚合统一于一体,既达到了充分利用光能的目的,又达到了互相改性的目的,其固化产物集中了环氧树脂和丙烯酸酯各自的优点,同时又克服了某些缺陷,开创了一个全新的体系。用二苯甲基碘鎓六氟磷酸盐(DPI.PF6)作光引发剂,引发双酚A环氧树脂E51和丙烯酸酯预聚物AE的混合树脂制得了低粘度、固化时间短、胶接层剪切强度高、耐水煮沸性好的胶粘剂,使环氧树脂和丙烯酸酯的优势都显示了出来。以下列举了几种混合体系的组成:Because the photoinitiated cationic polymerization system has defects such as unsatisfactory photoinitiation, slow curing speed, and high cost, which limit its promotion in industry, some people have unified the cationic polymerization of epoxy resin and the free radical polymerization of acrylate, both to achieve In order to make full use of light energy, it also achieves the purpose of mutual modification. Its cured product combines the advantages of epoxy resin and acrylate, and overcomes some defects at the same time, creating a new system. Using diphenylmethyl iodonium hexafluorophosphate (DPI.PF 6 ) as photoinitiator, the mixed resin of bisphenol A epoxy resin E 51 and acrylate prepolymer AE was prepared to obtain low viscosity, short curing time, Adhesives with high shear strength and good water boiling resistance of the bonding layer make the advantages of epoxy resin and acrylate come out. The composition of several mixed systems is listed below:

1、环氧树脂E-51(双酚A(2,2-双(4-羟基苯基)丙烷))和环氧氯丙烷在碱性介质中缩聚合成的线型聚合物,(51代表环氧的比例分数50%),二芳基碘鎓盐(CD-1012),光敏剂二异丙基噻唑酮(ITX)组成的阳离子光引发体系。1. Epoxy resin E-51 (linear polymer formed by condensation of bisphenol A (2,2-bis(4-hydroxyphenyl) propane)) and epichlorohydrin in alkaline medium, (51 represents cyclo Oxygen proportion fraction 50%), diaryliodonium salt (CD-1012), photosensitizer diisopropylthiazolone (ITX) composed of cationic photoinitiation system.

2、双酚A环氧树脂(环氧树脂128),阳离子引发剂硫鎓离子六氟磷酸盐(6992)和硫鎓离子六氟锑酸盐(6976)为硫鎓盐,活性稀释剂丁基缩水甘油醚(669),长碳链缩水甘油醚(114),羟基单体(0200),二官能和三官能的聚己内酯多元醇(0301)。2. Bisphenol A epoxy resin (epoxy resin 128), cationic initiator sulfonium ion hexafluorophosphate (6992) and sulfonium ion hexafluoroantimonate (6976) are sulfonium salts, reactive diluent butyl Glycidyl ether (669), long carbon chain glycidyl ether (114), hydroxyl monomer (0200), difunctional and trifunctional polycaprolactone polyol (0301).

3、一将甲基丙烯酸酯/甲基丙烯酸缩水甘油酯共聚物接枝到聚氨酯上,经胺中和后制得自乳化型丙烯酸树脂接枝聚氨酯,增强了聚氨酯与丙烯酸树脂的相容性,提高了树脂的性价比。3. Graft methacrylate/glycidyl methacrylate copolymer to polyurethane, and then neutralize with amine to obtain self-emulsifying acrylic resin grafted polyurethane, which enhances the compatibility of polyurethane and acrylic resin, The cost performance of the resin is improved.

4、三缩四乙二醇二甲基丙烯酸酯、三缩四乙二醇二甲基丙烯酸酯分别与3,4-环氧环己基甲基-3′,4′-环氧环己烷羧酸酯混合,光引发剂为α-羟基环己基苯酮(Irgacure184)、2,2-二甲氧基-2-苯基苯乙酮(Irgacure651)、安息香二甲醚、六氟磷酸二苯基碘鎓盐。4. Tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate respectively Ester mixed, the photoinitiator is α-hydroxycyclohexyl phenone (Irgacure184), 2,2-dimethoxy-2-phenylacetophenone (Irgacure651), benzoin dimethyl ether, diphenyl hexafluorophosphate iodonium salt.

5、2-乙二醇烯丙基醚和环氧丙烯酸树脂(CG602)混合体,阳离子型光引发剂二甲苯基碘鎓盐或自由基型光引发剂2,2-二甲氧基-2-苯基苯乙酮(Irgacure651)或2-羟基-2-甲基苯丙酮(Darocur1173)。5. Mixture of 2-ethylene glycol allyl ether and epoxy acrylic resin (CG602), cationic photoinitiator xylyliodonium salt or free radical photoinitiator 2,2-dimethoxy-2 - Phenylacetophenone (Irgacure651) or 2-Hydroxy-2-methylpropiophenone (Darocur1173).

6、4-环氧环己基甲酸-3,4-环氧环己基甲基酯(CY179)、己内酯三元醇、三芳基硫盐、二苯酮及丙烯酸酯单体。6. 3,4-epoxycyclohexylmethyl 4-epoxycyclohexylcarboxylate (CY179), caprolactone triol, triaryl sulfide, benzophenone and acrylate monomer.

7、乙烯基醚类化合物具有固化速度快、粘度低、不怕氧气阻聚、无味、无毒的优点。以丙烯酸酯齐聚物、三缩乙二醇二乙烯基醚、二甲苯基碘鎓盐、α-羟基环己基苯酮(Irgacure184)组成的混杂光固化体系具有固化速度快、耐溶剂性能好、无需“后固化”及对聚酯基材附着力好等特点。7. Vinyl ether compounds have the advantages of fast curing speed, low viscosity, no fear of oxygen inhibition, tasteless and non-toxic. The hybrid photocuring system composed of acrylate oligomer, triethylene glycol divinyl ether, xylyl iodonium salt, and α-hydroxycyclohexyl phenone (Irgacure184) has fast curing speed, good solvent resistance, Features such as no need for "post-cure" and good adhesion to polyester substrates.

以下是本发明的具体实施例:The following are specific embodiments of the present invention:

实施例1Example 1

如图1所示,衬底1为玻璃,阳极缓冲层3为PEDOT:PSS(10nm),阴极缓冲层5为TPBi(10nm),金属阴极6为Ag(100nm)。光活性层4为PCDTBT:PCBM(1:20,40nm)中掺有紫外敏感胶,紫外敏感胶在光活性层中所占的质量比为0.03%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is glass, the anode buffer layer 3 is PEDOT:PSS (10nm), the cathode buffer layer 5 is TPBi (10nm), and the metal cathode 6 is Ag (100nm). The photoactive layer 4 is PCDTBT: PCBM (1:20, 40nm) is doped with UV-sensitive glue, the mass ratio of UV-sensitive glue in the photoactive layer is 0.03%, and the UV-sensitive glue is free radical type UV-sensitive glue and Mixed system of cationic UV sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的玻璃衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared glass substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:97%的基础树脂、1%的单体、1%的光引发剂和1%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括97%的阳离子单体、2%的稀释剂和1%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 97% base resin, 1% monomer, 1% photoinitiator and 1% photosensitizer and auxiliary agent; Cationic UV-sensitive rubber raw materials include 97% cationic monomer, 2% diluent and 1% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

实施例2Example 2

如图1所示,衬底1为玻璃,阳极缓冲层3为PEDOT:PSS(40nm),阴极缓冲层5为TPBi(1nm),金属阴极6为Ag(300nm)。光活性层4为PCDTBT:PCBM(5:1,250nm)中掺有紫外敏感胶,所述紫外敏感胶在光活性层中所占的质量比为0.05%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is glass, the anode buffer layer 3 is PEDOT:PSS (40nm), the cathode buffer layer 5 is TPBi (1nm), and the metal cathode 6 is Ag (300nm). The photoactive layer 4 is PCDTBT:PCBM (5:1, 250nm) mixed with UV-sensitive glue, the mass ratio of the UV-sensitive glue in the photoactive layer is 0.05%, and the UV-sensitive glue is free radical UV-sensitive A mixed system of glue and cationic UV-sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的玻璃衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared glass substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:97.5%的基础树脂、0.2%的单体、0.3%的光引发剂和2%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括97.5%的阳离子单体、0.5%的稀释剂和2%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 97.5% base resin, 0.2% monomer, 0.3% photoinitiator and 2% photosensitizer and auxiliary agent; Cationic UV-sensitive adhesive raw materials include 97.5% cationic monomer, 0.5% diluent and 2% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

实施例3Example 3

如图1所示,衬底1为玻璃,阳极缓冲层3为PEDOT:PSS(80nm),阴极缓冲层5为TPBi(8nm),金属阴极6为Ag(150nm)。光活性层4为PCDTBT:PCBM(1:1,200nm)中掺有紫外敏感胶,所述紫外敏感胶在光活性层中所占的质量比为0.1%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is glass, the anode buffer layer 3 is PEDOT:PSS (80nm), the cathode buffer layer 5 is TPBi (8nm), and the metal cathode 6 is Ag (150nm). The photoactive layer 4 is PCDTBT:PCBM (1:1, 200nm) mixed with UV-sensitive glue, the mass ratio of the UV-sensitive glue in the photoactive layer is 0.1%, and the UV-sensitive glue is free radical UV-sensitive A mixed system of glue and cationic UV-sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的玻璃衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared glass substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:98%的基础树脂、0.9%的单体、0.1%的光引发剂和1%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括98%的阳离子单体、1.5%的稀释剂和0.5%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 98% base resin, 0.9% monomer, 0.1% photoinitiator and 1% photosensitizer and auxiliary agent; Cationic UV-sensitive adhesive raw materials include 98% cationic monomer, 1.5% diluent and 0.5% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

实施例4Example 4

如图1所示,衬底1为玻璃,阳极缓冲层3为PEDOT:PSS(20nm),阴极缓冲层5为TPBi(8nm),金属阴极6为Ag(150nm)。光活性层4为PCDTBT:PCBM(1:1,200nm)中掺有紫外敏感胶,所述紫外敏感胶在光活性层中所占的质量比为0.5%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is glass, the anode buffer layer 3 is PEDOT:PSS (20nm), the cathode buffer layer 5 is TPBi (8nm), and the metal cathode 6 is Ag (150nm). The photoactive layer 4 is PCDTBT:PCBM (1:1, 200nm) mixed with UV-sensitive glue, the mass ratio of the UV-sensitive glue in the photoactive layer is 0.5%, and the UV-sensitive glue is free radical UV-sensitive A mixed system of glue and cationic UV-sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的玻璃衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared glass substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:98.5%的基础树脂、0.2%的单体、0.4%的光引发剂和0.9%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括98.5%的阳离子单体、1%的稀释剂和0.5%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 98.5% base resin, 0.2% monomer, 0.4% photoinitiator and 0.9% photosensitizer and auxiliary agent; Cationic UV-sensitive rubber raw materials include 98.5% cationic monomer, 1% diluent and 0.5% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

实施例5Example 5

如图1所示,衬底1为玻璃,阳极缓冲层3为PEDOT:PSS(20nm),阴极缓冲层(5)为TPBi(8nm),金属阴极6为Ag(150nm)。光活性层4为PCDTBT:PCBM(1:1,200nm)中掺有紫外敏感胶,所述紫外敏感胶在光活性层中所占的质量比为1%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is glass, the anode buffer layer 3 is PEDOT:PSS (20nm), the cathode buffer layer (5) is TPBi (8nm), and the metal cathode 6 is Ag (150nm). The photoactive layer 4 is PCDTBT:PCBM (1:1, 200nm) mixed with UV-sensitive glue, the mass ratio of the UV-sensitive glue in the photoactive layer is 1%, and the UV-sensitive glue is free radical UV-sensitive A mixed system of glue and cationic UV-sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的玻璃衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared glass substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:99%的基础树脂、0.5%的单体、0.2%的光引发剂和0.3%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括99%的阳离子单体、0.5%的稀释剂和0.5%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 99% base resin, 0.5% monomer, 0.2% photoinitiator and 0.3% photosensitizer and auxiliary agent; Cationic UV-sensitive adhesive raw materials include 99% cationic monomer, 0.5% diluent and 0.5% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

实施例6Example 6

如图1所示,衬底1为玻璃,阳极缓冲层3为PEDOT:PSS(20nm),阴极缓冲层5为TPBi(8nm),金属阴极6为Ag(150nm)。光活性层4为PCDTBT:PCBM(1:1,200nm)中掺有紫外敏感胶,所述紫外敏感胶在光活性层中所占的质量比为3%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is glass, the anode buffer layer 3 is PEDOT:PSS (20nm), the cathode buffer layer 5 is TPBi (8nm), and the metal cathode 6 is Ag (150nm). The photoactive layer 4 is PCDTBT:PCBM (1:1, 200nm) mixed with UV-sensitive glue, the mass ratio of the UV-sensitive glue in the photoactive layer is 3%, and the UV-sensitive glue is free radical UV-sensitive A mixed system of glue and cationic UV-sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的玻璃衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared glass substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:99.5%的基础树脂、0.2%的单体、0.1%的光引发剂和0.2%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括99.5%的阳离子单体、0.4%的稀释剂和0.1%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 99.5% base resin, 0.2% monomer, 0.1% photoinitiator and 0.2% photosensitizer and auxiliary agent; Cationic UV-sensitive adhesive raw materials include 99.5% cationic monomer, 0.4% diluent and 0.1% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

实施例7Example 7

如图1所示,衬底1为柔性聚对苯二甲酸乙二醇酯(PET)衬底,阳极缓冲层3为PEDOT:PSS(20nm),阴极缓冲层5为TPBi(8nm),金属阴极6为Ag(150nm)。光活性层4为PCDTBT:PCBM(1:1,200nm)中掺有紫外敏感胶,所述紫外敏感胶在光活性层中所占的质量比为6%,紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。As shown in Figure 1, the substrate 1 is a flexible polyethylene terephthalate (PET) substrate, the anode buffer layer 3 is PEDOT:PSS (20nm), the cathode buffer layer 5 is TPBi (8nm), and the metal cathode 6 is Ag (150nm). The photoactive layer 4 is PCDTBT:PCBM (1:1, 200nm) mixed with UV-sensitive glue, the mass ratio of the UV-sensitive glue in the photoactive layer is 6%, and the UV-sensitive glue is free radical UV-sensitive A mixed system of glue and cationic UV-sensitive glue.

制备方法如下:The preparation method is as follows:

①先对预先制备好透明导电阳极ITO的PET衬底进行彻底的清洗,清洗后干燥;① Thoroughly clean the pre-prepared PET substrate of the transparent conductive anode ITO, and dry it after cleaning;

②在透明导电阳极ITO表面旋转涂覆PEDOT:PSS溶液并将所形成的薄膜进行退火处理;② Spin-coat PEDOT:PSS solution on the surface of transparent conductive anode ITO and anneal the formed film;

③在阳极缓冲层表面旋转涂覆掺有紫外敏感胶的PCDTBT:PCBM溶液制备光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系,所述自由基型紫外敏感胶的原料包括以下成份:97%的基础树脂、1%的单体、1%的光引发剂和1%的光敏剂以及助剂;所述阳离子型紫外敏感胶原料包括97%的阳离子单体、2%的稀释剂和1%的阳离子光引发剂;③The surface of the anode buffer layer is spin-coated with PCDTBT:PCBM solution mixed with UV-sensitive glue to prepare the photoactive layer, and the formed film is annealed. The UV-sensitive glue is free radical UV-sensitive glue and cationic UV-sensitive glue. The mixed system of sensitive glue, the raw material of described radical type ultraviolet sensitive glue comprises following composition: 97% base resin, 1% monomer, 1% photoinitiator and 1% photosensitizer and auxiliary agent; Cationic UV-sensitive rubber raw materials include 97% cationic monomer, 2% diluent and 1% cationic photoinitiator;

④对步骤③得到的光活性层进行紫外光处理30秒;④UV treatment of the photoactive layer obtained in step ③ for 30 seconds;

⑤在光活性层表面蒸镀阴极缓冲层TPBi;⑤ Evaporate the cathode buffer layer TPBi on the surface of the photoactive layer;

⑥在阴极缓冲层表面蒸镀金属阴极Ag。⑥Vapor-deposit metal cathode Ag on the surface of the cathode buffer layer.

表1为采用PET作为衬底的有机薄膜太阳能电池的性能比较,一种是在光活性层中加入紫外敏感胶的有机薄膜太阳能电池,一种是未添加紫外敏感胶的有机薄膜太阳能电池。其中,弯曲半径为10mm,方向为向外弯曲。Table 1 shows the performance comparison of organic thin film solar cells using PET as the substrate. One is the organic thin film solar cell with UV-sensitive glue added to the photoactive layer, and the other is the organic thin-film solar cell without UV-sensitive glue. Wherein, the bending radius is 10mm, and the direction is outward bending.

表1Table 1

Claims (3)

1.一种有机薄膜太阳能电池,其特征在于,该太阳能电池结构从下到上依次为衬底(1)、透明导电阳极ITO(2)、阳极缓冲层(3)、光活性层(4)、阴极缓冲层(5)和金属阴极(6),所述光活性层(4)中掺有质量比为0.03-6%的紫外敏感胶;所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系。 1. An organic thin-film solar cell, characterized in that the structure of the solar cell from bottom to top is a substrate (1), a transparent conductive anode ITO (2), an anode buffer layer (3), and a photoactive layer (4) , a cathode buffer layer (5) and a metal cathode (6), the photoactive layer (4) is doped with a UV-sensitive glue with a mass ratio of 0.03-6%; the UV-sensitive glue is a free radical type UV-sensitive glue and Mixed system of cationic UV sensitive glue. 2.根据权利要求1所述的有机薄膜太阳能电池,其特征在于,所述混合体系原料包括环氧树脂E-51,二芳基碘鎓盐和二异丙基噻唑酮。 2 . The organic thin film solar cell according to claim 1 , wherein the mixed system raw materials include epoxy resin E-51, diaryliodonium salt and diisopropylthiazolone. 3.一种有机薄膜太阳能电池的制备方法,其特征在于,包括以下步骤: 3. A method for preparing an organic thin film solar cell, comprising the following steps: ①先对预先制备好透明导电阳极ITO的衬底进行清洗,清洗后干燥; ① Clean the pre-prepared transparent conductive anode ITO substrate, and dry it after cleaning; ②在透明导电阳极ITO表面旋转涂覆、印刷或喷涂阳极缓冲层,并将所形成的薄膜进行退火处理; ② Spin-coat, print or spray-coat the anode buffer layer on the surface of the transparent conductive anode ITO, and anneal the formed film; ③在阳极缓冲层表面旋转涂覆、印刷或喷涂掺有质量比为0.03-6%的紫外敏感胶的光活性层,并将所形成的薄膜进行退火处理,所述紫外敏感胶为自由基型紫外敏感胶和阳离子型紫外敏感胶的混合体系; ③ On the surface of the anode buffer layer, spin coating, printing or spraying a photoactive layer mixed with a mass ratio of 0.03-6% UV-sensitive glue, and annealing the formed film, the UV-sensitive glue is free radical type Mixed system of UV-sensitive glue and cationic UV-sensitive glue; ④对步骤③得到的光活性层进行紫外光处理; ④ carrying out ultraviolet light treatment to the photoactive layer obtained in step ③; ⑤在光活性层表面蒸镀、旋转涂覆或喷涂阴极缓冲层; ⑤Evaporation, spin coating or spray coating of the cathode buffer layer on the surface of the photoactive layer; ⑥在阴极缓冲层表面蒸镀金属阴极。 ⑥Vapor-deposit a metal cathode on the surface of the cathode buffer layer.
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