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光引發(fā)劑:自由基型和陽(yáng)離子型的適用范圍
更新日期: 2020-10-14 |
光引發(fā)劑,又稱(chēng)光敏劑或光固化劑,通常用于光固化體系中,包括UV膠,UV涂料,UV油墨等,是一類(lèi)能在紫外光區(qū)(250~420nm)或可見(jiàn)光區(qū)(400~800nm)吸收一定波長(zhǎng)的能量,產(chǎn)生自由基、陽(yáng)離子等,從而引發(fā)單體聚合交聯(lián)固化的化合物。
Photoinitiators, also known as photosensitizers or photocuring agents, are commonly used in photocuring systems, such as UV adhesives, UV coatings, UV inks, etc. They absorb a certain wavelength of energy in the ultraviolet light region (250-420nm) or visible light region (400-800nm), which can generate free radicals, cations and some others, thereby initiating polymerization, crosslinking and curing of monomers.
南通新納希新材料有限公司多年從事光引發(fā)劑等產(chǎn)品業(yè)務(wù),質(zhì)量穩(wěn)定,價(jià)格極有競(jìng)爭(zhēng)力,現(xiàn)已銷(xiāo)往海內(nèi)外許多國(guó)家。
Nantong Synasia New Material Co., Ltd. has many years of experience in photoinitiators and other products. Due to stable quality and extremely competitive price, our products have been sold to numerous countries at home and abroad.
自由基型光引發(fā)劑 / Free-Radical Photoinitiator
按光引發(fā)劑產(chǎn)生活性自由基的作用機(jī)理不同,自由基型光引發(fā)劑主要分為以下兩類(lèi):
Depending on their reaction, free-radical photoinitiators are mainly divided into the following two categories:
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裂解型自由基型光引發(fā)劑
(Norrish Type I photoinitiator)
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奪氫型光引發(fā)劑
(Norrish Type II photoinitiator)
裂解型自由基光引發(fā)劑多以芳基烷基酮衍生物為主,比較有代表性的包括苯偶姻衍生物、苯偶??s酮衍生物、二烷氧基苯乙酮、α-羥烷基苯酮、α-胺烷基苯酮、?;浠?、酯化肟酮化合物、芳基過(guò)氧酯化合物、鹵代甲基芳酮、有機(jī)含硫化合物、苯甲酰甲酸酯等。
Norrish Type?I photoinitiators, also called cleavage-type free radical photoinitiators, are mostly aryl alkyl ketone derivatives. Representative ones include benzoin derivatives, benzil ketal derivatives, dialkoxy acetophenone, α-hydroxyl alkyl phenone, α-aminoalkyl phenone, acyl phosphine hydride, esterified oxime ketone compound, aryl peroxy ester compound, halogenated methyl aryl ketone, organic sulfur compound, benzoyl formate, etc.
奪氫型光引發(fā)劑一般以芳香酮結(jié)構(gòu)為主,還包括某些稠環(huán)芳烴,它們具有一定吸光性能,而與之匹配的助引發(fā)劑,即氫供體,本身在常用長(zhǎng)波紫外光范圍內(nèi)無(wú)吸收。奪氫型光引發(fā)劑吸收光能,在激發(fā)態(tài)與助引發(fā)劑發(fā)生雙分子作用,產(chǎn)生活性自由基。
Norrish Type II photoinitiators, also called hydrogen abstraction type photoinitiators, are generally based on aromatic ketone structures, and also include certain fused-ring aromatic hydrocarbons, which have certain light absorption properties, and the matching co-initiator, namely hydrogen donor, itself is not absorpted in the range of commonly used long-wave ultraviolet light. The hydrogen abstraction type photoinitiator absorbs light energy and has bimolecular interaction with the co-initiator in the excited state to generate active free radicals.
新納希生產(chǎn)的光引發(fā)劑KIP-100F由1173和KIP-150組成。
The photoinitiator KIP-100F produced by Synasia is composed of 1173 and KIP-150.
從結(jié)構(gòu)上看,1173屬于苯乙酮衍生物,是一類(lèi)自由基型光引發(fā)劑。由于1173是液體,非常易于共混,所以適合與其它光引發(fā)劑復(fù)配使用。對(duì)于不飽和聚酯體系和多官能團(tuán)單體的UV固化體系,1173具有低氣味、不黃變、色彩穩(wěn)定性好等特點(diǎn),可用于紙張、金屬和塑料表面的丙烯酸酯系列的紫外光固化清漆。特別推薦用于要求即使長(zhǎng)時(shí)間暴露于太陽(yáng)光下也只有細(xì)微黃變的UV涂料。
According to its structure, 1173 is a derivative of acetophenone. It belongs to a kind of free radical photoinitiator. As a liquid, 1173 is very easy to blend, suitable for compounding with other photoinitiators. For the UV curing system of unsaturated polyester systems and multifunctional monomers, 1173 has the characteristics of low odor, non-yellowing property and good color stability. It can be used for UV curing varnishes of acrylic ester series on paper, metal and plastic surfaces. It is especially recommended for UV coatings that require only slight yellowing even when exposed to sunlight for a long time.
UV固化體系中,小分子型的光引發(fā)劑在保存過(guò)程中,容易揮發(fā)和遷移.這一方面會(huì)降低光聚合引發(fā)效率,另一方面會(huì)導(dǎo)致產(chǎn)品出現(xiàn)氣味和毒性。尤其是在食品包裝袋上印刷的光固化油墨都嚴(yán)禁小分子光引發(fā)劑或光敏劑發(fā)生遷移,否則會(huì)透過(guò)食品袋污染內(nèi)部食品。將小分子光引發(fā)劑鍵合到高分子鏈上,即可減小這種遷移作用。因此高分子型光引發(fā)劑已成為重要的研究發(fā)展方向。
In the UV curing system, small molecular photoinitiators are easy to volatilize and migrate during storage. On the one hand, it will reduce the initiation efficiency of photo-polymerization, and on the other hand, it may cause odor and toxicity of the product. In particular, the photocurable ink printed on food packaging bags is strictly prohibited from migrating small molecule photoinitiators or photosensitizers, otherwise it will pollute the internal food through the food bags. Bonding the small molecule photoinitiator to the polymer chain can reduce this migration effect. Therefore, polymeric photoinitiators have become an important research and development direction.
KIP-150是一種高分子型光引發(fā)劑,與樹(shù)脂體系的混溶性較好,低揮發(fā)、低遷移,還可制成水乳液,成為水性光固化引發(fā)劑。KIP-150分子鏈上含有多個(gè)引發(fā)劑單元,光輻照時(shí)可在一個(gè)大分子上同時(shí)形成多個(gè)自由基,局部自由基濃度可以很高。局部高濃度效應(yīng)可以有效對(duì)付氧阻聚,有利于加速光聚合,但大分子內(nèi)活性自由基相互互偶合終止的幾率也會(huì)增加,通過(guò)設(shè)計(jì)分子結(jié)構(gòu),可以降低分子內(nèi)自由基偶合。
KIP-150 is a polymeric photoinitiator with good miscibility with resin systems, which provides low volatility and low migration. It can also be made into water emulsion and used as water-based photocuring initiator. The molecular chain of KIP-150 contains multiple initiator units, which can simultaneously form multiple free radicals on one macromolecule when irradiated by light, and the local free radical concentration can be very high. The local high concentration effect can effectively deal with oxygen inhibition and accelerate photopolymerization, but the probability of mutual coupling termination of active free radicals in macromolecules will also increase. By designing molecular structure, intramolecular free radical coupling can be reduced.
基于高反應(yīng)性、低氣味和顏色穩(wěn)定性佳的特點(diǎn),KIP-100F通常應(yīng)用于各類(lèi)涂料和膠粘劑等,涉及行業(yè)包括塑料、木器、金屬等。
Due to the characteristics of high reactivity, low odor and good color stability, KIP-100F is generally used in various coatings and adhesives, etc. It involves in industries like plastics, wood, metal, etc.
陽(yáng)離子型光引發(fā)劑是另一類(lèi)非常重要的光引發(fā)劑,包括重氮鹽、二芳基碘鎓鹽、三芳基硫鎓鹽、烷基硫鎓鹽、鐵芳烴鹽、磺酰氧基酮及三芳基硅氧醚。適用于陽(yáng)離子光聚合的單體主要有環(huán)氧化合物、乙烯基醚,其次還有內(nèi)酯、縮醛、環(huán)醚等。
Cationic photoinitiators are also very important type of photoinitiators, including diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron aromatic hydrocarbon salts, sulfonyloxy ketones and triarylsiloxane ether. They are suitable for cationic photopolymerization with monomers which mainly include epoxy compounds and vinyl ethers, followed by lactones, acetals, cyclic ethers, etc.
南通新納希新材料有限公司提供兩款陽(yáng)離子型光引發(fā)劑,分別是UVI-6976和UVI-6992,適配新納希明星產(chǎn)品——脂環(huán)族環(huán)氧樹(shù)脂(牌號(hào)S-06E或S-21),以及新納希氧雜環(huán)丁烷類(lèi)產(chǎn)品(牌號(hào)S-101或S-221),在微電子以及信息材料中具有廣泛應(yīng)用。
Nantong Synasia New Material Co., Ltd. provides two different cationic photoinitiators, UVI-6976 and UVI-6992, which are suitable for use with Synasia cycloaliphatic epoxy resin (S-06E or S- 21), as well as Synasia oxetane product (S-101 or S-221). Our products are widely used in microelectronics and information materials.
UVI-6976
UVI-6976是一種混合型三芳基六氟銻酸锍鎓鹽陽(yáng)離子引發(fā)劑,主要用于含環(huán)氧基團(tuán)體系的固化。具有引發(fā)速度快、內(nèi)應(yīng)力小、后固化深層固化好等顯著特點(diǎn)。應(yīng)用于印刷電路板、液晶顯示屏和大規(guī)模集成電路等尖端制造業(yè)。
UVI-6976 is a mixed type triaryl sulfonium hexafluoroantimonate cationic photoinitiator, mainly used for curing systems which contain epoxy groups. It has the remarkable characteristics of fast initiation speed, low internal stress and excellent deep curing. Applications include cutting-edge manufacturing industries, such as printed circuit boards, liquid crystal displays and large-scale integrated circuits.
UVI-6992是一種混合型三芳基六氟磷酸锍鎓鹽陽(yáng)離子引發(fā)劑,通常也用于含環(huán)氧基團(tuán)體系的固化,應(yīng)用也和UVI-6976相同。作為兩種三芳基锍鎓鹽陽(yáng)離子引發(fā)劑,當(dāng)引發(fā)劑濃度較低時(shí),UVI-6976的引發(fā)活性遠(yuǎn)遠(yuǎn)高于UVI-6992,但是當(dāng)引發(fā)劑濃度較高時(shí),二者的引發(fā)活性相近,兩種引發(fā)體系得到的聚合物體積收縮均較低。通常應(yīng)用于油墨、粘合劑和以鈦白粉為顏料的厚涂層。
UVI-6992 is a mixed triacylsulfonium hexafluorophosphate cationic photoinitiator. Similar to UVI-6976, it is also used for curing epoxy systems. When the initiator concentration is low, the initiating activity of UVI-6976 is much higher than that of UVI-6992, but when the initiator concentration is high, the initiating activity of the two is similar. The volume shrinkage of the polymer obtained by the two initiation systems is lower. Our product is usually applied in inks, adhesives and thick coatings which use titanium dioxide as pigment.
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