CN114105943A - 3-位取代硫杂蒽酮化合物及其制备方法和光聚合体系应用 - Google Patents
3-位取代硫杂蒽酮化合物及其制备方法和光聚合体系应用 Download PDFInfo
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- CN114105943A CN114105943A CN202010912443.3A CN202010912443A CN114105943A CN 114105943 A CN114105943 A CN 114105943A CN 202010912443 A CN202010912443 A CN 202010912443A CN 114105943 A CN114105943 A CN 114105943A
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- C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
- C07D335/12—Thioxanthenes
- C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
- C07D335/16—Oxygen atoms, e.g. thioxanthones
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
本发明涉及有机功能新材料化学品领域,首次披露了一类新奇的3‑位取代的硫杂蒽酮类新结构化合物,其制备方法,以及含有该类化合物的辐射固化配方材料体系及其应用。这些硫杂蒽酮物质是重要的含烯不饱和体系光聚合过程的光敏引发剂关键精细化学品。
Description
【技术领域】
本发明涉及有机功能新材料化学品领域,首次披露了一类新奇的3-位取代的硫杂蒽酮类新结构化合物,其制备方法,以及含有该类化合物的辐射固化配方材料体系及其应用。这些硫杂蒽酮物质是重要的含烯不饱和体系光聚合过程的光敏引发剂(Photo-initiator)关键精细化学品。
【背景技术】
一些硫杂蒽酮类化合物由于其优异的紫外及可见光宽泛吸收性能,是已知的应用广泛的光引发剂化合物和/或光敏化剂(Sensitizer)化合物,代表性产品是例如已经商业化的品牌为ITX或DETX,其相应的化学结构特征分别是2-位或4-位异丙基取代的硫杂蒽酮,和2-位与4-位同时乙基取代的硫杂蒽酮。
迄今为止,3-位取代的硫杂蒽酮型化合物尚未见文献报道,也从未被用作光敏引发剂。这是一类新型结构的化合物,且被理论预言为具备比其他硫杂蒽酮异构体(例如2-位和4-位异构体)更高的光敏引发活性【N.S.Allen,et.al J.Oil.Colour.Chem.Assoc.1987,70(11),332】。
对从业技术人员而言,3-位取代的硫杂蒽酮型化合物未被应用缘由是显而易见的,因为硫杂蒽酮型化合物的既有文献制备方法批露,通常使用二硫代水杨酸起始原料和烷基苯在强质子酸介质中发生芳环亲电加成和氧化环合技术,而芳环亲电加成的烷基定位化学选择性规则决定了只可能生成2-位及连带的4-位硫杂蒽酮异构体,而不可能由此制备3-位取代的硫杂蒽酮异构体;合成后者以及探索其未知性能是本领域从业技术人员期望但尚未解决的重要课题之一。
【发明内容】
本项申请首次实现了通式(I)所示3-位取代的硫杂蒽酮化合物的制备,同时发现该类化合物是性能优异的光敏化剂和光引发剂化合物。定义R0是一个含有1-24个碳原子(标记为C1-C24)的支链或直链或环状的烷烃或取代或非取代的(杂)芳烃基,处于硫杂蒽酮环系3-位的R1基是OH,SH,卤素原子,R0,OR0,SR0,NHR0,或N(R0)2;R2-R8基取值彼此独立地是R1或氢;
符合通式(I)定义的化合物的示例性而非限定性结构如下:
通式(I)化合物的制备方法之一披露如下,其涉及酰卤化(自A至B),傅-克酰基化(B和C反应生成D),氧化(自D至E),和环合四步反应生产目标产物(I)。由于R1基团的推电子特性(Electron-donating Effect),在该工艺过程中,关键中间体化合物D的酰基化准确定位在R1基团的对位位置,因此产物呈现出3-位R1基团精准取代的新化合物结构。
其中R是氢,C1-C24直链或支链或环状烷基,或取代或未取代芳基;X和Y彼此独立地是氯或溴;酰卤化试剂是三卤化磷(PX3),二氯亚砜,氯气,草酰氯,或形式为Q-CX3的三卤化物(反应通式为RCO2H+Q-CX3=RC(O)X+Q-C(O)X+HX),其中Q是C1-C16烷基或芳基;氧化剂是氯气,二氯亚砜,磺酰氯,金属卤化物盐。
通式(I)化合物的制备方法之二披露如下,其涉及酰卤化(自F至G),傅-克酰基化(G和C反应生成E),氧化(自E至H),和环合四步反应生产目标产物(I)。在该工艺过程中,同样关键中间体化合物E的酰基化准确定位在R1基团的对位位置,因此产物呈现出3-位R1基团精准取代的新化合物结构。
其中T是R或C(O)R;酰卤化试剂是三卤化磷,二氯亚砜,氯气,或形式为Q-CX3的三卤化物;氧化剂是氯气,二氯亚砜,磺酰氯,金属卤化物盐。
通式(I)化合物的制备方法之三披露如下,其涉及傅-克酰基化(L和M反应生成N),氧化(自N至P),和环合四步反应生产目标产物(I)。在该工艺过程中,由于事先使用了对位取代的酰卤L原料,其反应产物自然呈现3-位R1基团精准取代的新化合物结构。
其中R’与R定义相同;Y是氯;
氧化剂是氯气,二氯亚砜,磺酰氯,金属卤化物盐。
本工艺所涉及的反应“溶剂”选自含有1-24个碳的取代或非取代的芳香烃,直链或支链的脂肪烃,(亚)砜,酰胺,醚,酯,酮,腈,羧酸,水,胺,离子液,超临界二氧化碳,或上述任意二者或二者以上类型溶剂组成的混合溶剂;优先的溶剂是二甲基亚砜,二甲基砜,苯甲基亚砜,苯甲基砜,环丁亚砜,环丁砜,三氯硅烷,二氯甲烷,二氯乙烷,氯仿,四氯化碳,苯,甲苯,二甲苯,三甲苯,四甲苯,乙腈,乙苯,二乙苯,氯苯,二氯苯,苯甲醚,硝基苯,庚烷,己烷,石油醚,二氧六环,四氢呋喃,甲基叔丁基醚,乙二醇二甲醚,双缩乙二醇二甲醚,三缩乙二醇二甲醚,丙二醇甲醚醋酸酯,三乙胺,三丁胺,二甲基异丙胺,吡啶,N,N-四甲基乙二胺,N-烷基吗啉,N-烷基吡咯,N,N-二甲基甲酰胺,甲酰吗啉,N,N-二乙基甲酰胺,N-甲基吡咯烷酮,或上述任意二者或二者以上溶剂组成的混合溶剂。该反应也可以仅选用少量甚至不选用任何常规的“溶剂”,而采用原料固相加热和/或研磨,和/或超声波和/或微波辐照促进,的方式进行。
本工艺所涉及的反应“温度”选自-70摄氏度至200摄氏度之间,优先的是选自-30摄氏度至180摄氏度之间,更优先的是选自-20摄氏度至150摄氏度之间。本工艺所涉及的反应“压力”选自0.001至200个标准大气压之间,优先的是选自0.1至100个标准大气压之间,更优先的是选自0.1至20个标准大气压之间。
本发明批露的3-位取代的硫杂蒽酮化合物被实践发现是性能优异的光敏化剂和光引发剂化合物。
我们同时批露一类新型的辐射固化新材料配方体系,其特征是:
(3)至少含有一种本发明通式(I)披露的光引发剂或其混合物;
(4)至少含有一种含烯键(C=C)不饱和化合物(单体或树脂)。
优选的,该配方体系中所含有的“至少一种本发明披露的光引发剂或其混合物”的添加量是0.001-50%质量百分比,更优选的是0.01-20%质量百分比。
优选的,该配方体系含有其他文献已知的光引发剂物质。
所述“文献已知的光引发剂物质”是下述任意一种光引发剂化合物或任意两种或两种以上光引发剂化合物组成的复配混合物:包括羟基酮型(Hydroxyketones),胺基酮型(Aminoketones),膦酰型(Acylphosphine Oxides),肟酯型(Oxime Esters),二苯甲酮型(Benzophenones),苯甲酰甲酸酯型(Phenylglyoxylates),硫杂蒽酮型(Thioxanthones),鎓盐型阳离子光引发剂(Sulfoniums或Iodoniums或Photo-Acid Generators,即所谓PAGs),或染料作为实质性光敏化剂(Dye Sensitizers)的光引发剂物质。光引发剂的例子是Darocur 1173,Irgacure 184,APi-180(深圳有为技术控股集团有限公司),APi-307(深圳有为技术控股集团有限公司),APi-308(深圳有为技术控股集团有限公司),APi-1206(深圳有为技术控股集团有限公司产品),APi-1207(深圳有为技术控股集团有限公司),Irgacure 2959,Irgacure MBF,Irgacure 127,Irgacure 651,Esacure KIP-150,EsacureKIP-160,Esacure KIP-1001,Esacure 01,Irgacure 907,Irgacure 500,Irgacure 2200,Irgacure 2022,Irgacure 4500,Irgacure 369,Irgacure 379,Irgacure 819,IrgacureTPO,Irgacure TPO-L,BP,甲基或乙基米蚩酮,Esacure TZT,Irgacure 754,Irgacure ITX,Irgacure DETX,Irgacure CPTX,Irgacure OXE-01,Irgacure OXE-02,Irgacure OXE-03,Irgacure OXE-03,Tronly 304(常州强力电子新材料股份有限公司),Tronly 305(常州强力电子新材料股份有限公司),Irgacure 250,ADEKA NCI-831(日本艾迪科株式会社),ADEKA N-1414(日本艾迪科株式会社),Irgacure 290,Irgacure 270,以及香豆素型染料光敏化剂等,上述体系也可以复配相应的助引发剂(Co-initiator),例如活性胺,和/或氢硅烷类活性氢给体型助引发剂。
所述含烯键(C=C)不饱和化合物(单体)是任何含烯键可聚合单体,包括但不限于(甲基)丙烯酸酯,丙烯醛,烯烃,共轭双烯烃,苯乙烯,马来酸酐,富马酸酐,乙酸乙烯酯,乙烯基吡咯烷酮,乙烯基咪唑,(甲基)丙烯酸,(甲基)丙烯酸衍生物例如(甲基)丙烯酰胺,乙烯基卤化物,亚乙烯基卤化物等。所述含烯键(C=C)不饱和化合物(树脂)是任何含烯键预聚物和低聚物,包括但不限于(甲基)丙烯酰官能基的(甲基)丙烯酸共聚物,聚氨酯甲酸酯(甲基)丙烯酸酯,聚酯(甲基)丙烯酸酯,不饱和聚酯,聚醚(甲基)丙烯酸酯,硅氧烷(甲基)丙烯酸酯,环氧树脂(甲基)丙烯酸酯等,以及上述物质的水溶性或水分散性的类似物。
所述功能性添加剂是合适的各类添加剂,为本领域技术人员所知晓的是如下各类添加剂,包括但不限于阻聚剂,活性胺助引发剂,流平剂,消泡剂,抗流挂剂,增稠剂,增粘剂,分散剂,抗静电剂,增溶剂,稀释剂,水或有机溶剂,抗菌剂,阻燃剂,无机或有机填充剂(例如纳米氧化铝,二氧化硅,碳酸钙,硫酸钡等)和/或着色剂(例如颜料或染料等),增强涂料油墨耐候性的紫外线吸收剂或/和光稳定剂,及上述组分的合适的水性分散体或水溶解性产品。
本发明披露的上述新型辐射固化材料配方体系,包括光固化涂料或油墨材料,配合各种不同的施工方式(例如喷涂,滚涂,淋涂,擦涂,浸涂等)和/或施工工序(例如腻子,底涂,上色,中涂,面涂等),在PCB油墨,激光直接成像(LDI)油墨,印刷包装油墨,木器家具,塑胶产品,印刷包装,喷墨打印,电子消费品,机动车辆内外饰,管道型材,工业地坪,建筑幕墙,3D打印增材制作,以及船舶或集装箱体等下游市场均具有极为广阔的应用价值。
特别有价值的示例性而非限定性应用例如,该等涂料或油墨用于制备着色和未着色的油漆和清漆、粉末涂料、PCB油墨、LDI油墨、印刷油墨、印版、胶粘剂、压敏胶粘剂、牙科组合物、凝胶涂料、电子器件用光致抗蚀剂、电锻抗蚀剂、蚀刻抗蚀剂、液态和干膜二者、焊接抗蚀剂、制造用于各种显示器应用的滤色器的抗蚀剂,制备等离子显示面板的制造方法中的结构、电致发光显示器和LCD的抗蚀剂,用于LCD、全息数据储存,用于包封电子组件的组合物,用于制备磁记录材料、微机械部件、波导、光学开关、锻覆掩膜、蚀刻掩膜、彩色打样体系、玻璃纤维电缆涂料、丝网印刷模版,用于借助立体光刻产生三维物体,作为图像记录材料,用于全息记录、微电子电路、脱色材料,用于图像记录材料的脱色材料,用于使用微胶囊的图像记录材料,作为光致抗蚀剂材料用于UV和可见激光直接成像体系,作为光致抗蚀剂材料用于形成印刷电路板的依序构建层中的介电层;特别地,使用上文所述的可光聚合组合物来制备着色和未着色的油漆和清漆、粉末涂料、印刷油墨(例如丝网印刷油墨、用于胶版、柔版或喷墨印刷的油墨)、印版、胶粘剂、密封件、灌封组分、牙科组合物、泡沫、模制复合物、复合材料组合物、玻璃纤维电缆涂料、丝网印刷模版,用于借助立体光刻产生三维物体,和作为图像记录材料、光致抗蚀剂组合物、脱色材料、用于图像记录材料的脱色材料,用于使用微胶囊的图像记录材料。
在实施例中我们将进一步说明。
【具体实施方式】
实施例:3-异丙基-7-甲基-硫杂蒽酮
称取5克4-甲基硫酚加入到100毫升单口烧瓶中,加入20毫升乙醇溶解后再加入0.23克NaOH和3.4毫升碘甲烷。室温搅拌3小时后TLC监测原料消耗完毕。旋干溶剂后,加入100毫升1M的NaOH溶液和100毫升乙酸乙酯振摇,分液将有机相旋干得淡黄色固体,收率95%。1H NMR(400MHz,CDCl3):δ=7.25(d,J=7.9Hz,2H),7.16(d,J=7.9,2H),2.51(s,3H),2.38(s,3H)。
称取5克4-异丙基苯甲酸加入到100毫升烧瓶中,加入20毫升二氯乙烷溶解后再加入4.3毫升二氯亚砜室温搅拌6小时后,TLC监测原料消耗完毕。旋干溶剂经减压蒸馏得无色油状液体,收率98%。
在氮气保护下,向100毫升烧瓶中加入8克4-异丙基苯甲酰氯,加入20毫升二氯乙烷搅拌溶解,0℃下加入0.64克无水AlCl3反应30分钟后加入4-甲基-苯甲硫醚室温反应6小时,反应用5%盐酸淬灭后二氯乙烷萃取三次,合并有机相,经柱层析得黄色油状液体,收率75%。1H NMR(400MHz,CDCl3):δ=7.73(d,J=4.0Hz,2H),7.34-7.24(m,4H),7.16(br s,1H),3.01-2.93(m,1H),2.38(s,3H),2.34(s,3H),1.28(d,J=3.2Hz,6H)。
将6克上述酰基化产物加入到100毫升三口烧瓶中,加入30毫升二氯乙烷溶解后缓缓滴加磺酰氯,室温搅拌3小时后TLC监测原料消失,用氮气吹扫旋干溶剂,收率95%。
将上述中间体用30毫升二氯甲烷搅拌溶解,冰浴下加入3.5克无水ZnCl2粉末后搅拌反应4小时。旋干溶剂后,加入100毫升15%HCl和100毫升二氯甲烷,分液将有机相旋干后经柱层析得白色固体,收率74%。1H NMR(400MHz,CDCl3):δ=8.46(d,J=20Hz,2H),7.53-7.41(m,4H),3.10-3.02(m,1H),2.49(s,3H),1.33(d,J=3.8Hz,6H)。
实施例:3-异丙基-硫杂蒽酮
称取20克2,2-二硫代水杨酸加入到250毫升的单口烧瓶中,加入150毫升冰醋酸溶解,加入13.5克锌粉后于120℃回流搅拌过夜后,TLC检测原料消耗完毕后将反应液加入100毫升1M HCl溶液,加入100毫升乙酸乙酯搅拌2小时,分液将有机相旋干得淡黄色固体,收率是定量的。
将20克硫代水杨酸加入到250毫升的单口烧瓶中,加入100毫升甲醇溶解后,加入12.5克NaOH搅拌30分钟,滴加8.5毫升碘甲烷。室温搅拌6小时,TLC检测原料反应完毕。旋干溶剂后,加入100毫升1M HCl溶液,加入100毫升乙酸乙酯搅拌反应2h,分液将有机相旋干得白色固体,收率87%。1H NMR(400MHz,CDCl3):δ=8.15(dd,J=7.9,1.2Hz,1H),7.55-7.51(m,1H),7.30(d,J=7.9Hz,1H),7.20(t,J=3.8Hz,1H),2.48(s,3H)。
在氮气保护下,向250毫升烧瓶中依次加入10克上述化合物和100毫升二氯甲烷搅拌溶解,常温下加入40毫升草酰氯搅拌反应6小时反应完全,旋干溶剂得淡黄色固体产品。
将2克经由上述二氯亚砜作用新鲜制备的邻甲巯基水杨酰氯加入到100毫升单口烧瓶中,加入10毫升二氯甲烷溶解,然后加入1.9克无水A1C13搅拌30分钟后滴加1.24毫升异丙苯。冰浴搅拌6小时后TLC检测原料消耗完毕。旋干溶剂后,加入100毫升1M HCl(1mol/L)溶液,加入100毫升乙酸乙酯搅拌2小时,分液将有机相旋干得白色固体,收率92%。1HNMR(400MHz,CDCl3):δ=7.73(d,J=3.9,2H),7.47-7.28(m,5H),7.23-7.19(m,1H),3.00-2.94(m,1H),2.42(s,3H),1.27(d,J=3.4,6H)。
将2克上述化合物置于100毫升烧瓶中,加入30毫升二氯甲烷溶解后滴加加入2当量磺酰氯,室温搅拌6小时后,TLC监测反应完毕,旋干溶剂得到粗产品,收率95%。
向100毫升单口烧瓶中N2保护下加入2克上述原料,加入30毫升二氯甲烷搅拌溶解,冰浴下加入3.5克无水ZnCl2搅拌反应6小时,TLC监测原料消耗完毕。旋干溶剂后,加入5%浓度HCl溶液100毫升,再加入100毫升二氯甲烷搅拌30分钟,分液将有机相旋干得淡黄色固体,经柱层析得白色固体产品,收率68%。1H NMR(400MHz,CDCl3):δ=8.63(d,J=7.8,1H),8.50(s,1H),7.63-7.45(m,5H),3.11-3.02(m,1H),1.33(d,J=7.2,6H)。
实施例:1,3-二乙基-硫杂蒽酮
称取12.6克2,2-二硫代水杨酸和30毫升二氯亚砜混合回流反应3小时,浓缩后的酰氯粗产品直接用120毫升二氯乙烷稀释,依次加入9克间二乙苯和8.5克无水AlCl3粉末,搅拌反应6小时后,混合物用150毫升的1M HCl溶液分解,有机相滤过浓缩后,在乙醇中重结晶,得到7.4克双酰基化产物。
取5.5克上述双酰基化产物置于100毫升三口烧瓶中,加入30毫升二氯乙烷溶解后缓缓通入氯气,室温搅拌3小时后用氮气吹扫旋干溶剂。
将上述中间体用50毫升二氯甲烷重新搅拌溶解,冰浴下加入2.7克无水AlCl3粉末后搅拌反应4小时。旋干溶剂后,加入120毫升5%HCl和100毫升二氯甲烷,分液将有机相旋干后经柱层析得2.8克淡黄色固体产品。
实施例:光聚合引发活性性能
含烯键(丙烯酸酯)UV辐射固化材料配方体系样品按下列配方制作(以重量百分比计):双酚A环氧丙烯酸酯(Ebecryl 605):20%;胺改性丙烯酸酯:12%(活性胺树脂);氨基丙烯酸酯(Ebecryl 7100):10%;丙烯酰吗啉:55%;光引发剂:3%。
光固化性能评估:将上述样品涂覆于卡纸板上形成约20-25微米的涂层,以UV高压汞灯(距离基材约20厘米)为辐照光源,变速传送带试验。以指甲反复压刻刮擦不产生印迹为光聚合固化完成的判据。
结果如下:当光引发剂是3%的3-异丙基-7-甲基-硫杂蒽酮,光固化完全最大线速度为48米/分钟;当光引发剂是3%的3-异丙基-硫杂蒽酮,光固化完全最大线速度为45米/分钟;当光引发剂是3%的1,3-二乙基-硫杂蒽酮,光固化完全最大线速度为50米/分钟。上述试验展现了本发明批露化合物优异的光聚合引发活性。
含烯键可辐射固化PCB油墨材料体系样品按下列配方制作(以重量百分比计):A组分中,邻甲酚醛环氧丙烯酸酯齐聚物:55%;DBE溶剂:20%;光引发剂:4%;二氧化硅:1.5%;硫酸钡:11.5%;钛白粉:8%;B组分中,DPHA丙烯酸酯单体:35%;环氧树脂:35%;DBE溶剂:20%;硫酸钡:10%。将上述材料混合加入分散桶内,用高速分散机进行分散和液压三辊机研磨5次并滤芯过滤机过滤后,所得油墨用带有XAAR喷头的喷墨印刷机以80m/min的速度进行PCB板喷印,固化光源的线功率约为200W/cm。感光引发活性使用Stouffer型曝光标准21阶灰度尺量化标定。
光固化性能评估:当光引发剂是3.5%的Irgacure 907和0.5%的2-ITX,曝光灰阶度为9级;当光引发剂是3.5%的Irgacure 907和0.5%的3-ITX,曝光灰阶度为10级。上述试验展示了本发明批露化合物更高的感光灵敏度性能。
需要强调的是,上述实施例仅仅为示例性而非限定性说明,基于本项申请披露,任何从业技术人员所通常可能采用的反应条件或参数等调整或变动均不会偏离本发明的要旨,本专利的保护范围应以相关的权利书记载条目为准。
Claims (7)
6.一类新型的辐射固化新材料配方体系,其特征是:
(1)至少含有一种本发明通式(I)披露的光引发剂或其混合物;
(2)至少含有一种含烯键(C=C)不饱和化合物(单体或树脂)。
优选的,该配方体系中所含有的“至少一种本发明披露的光引发剂或其混合物”的添加量是0.001-50%质量百分比,更优选的是0.01-20%质量百分比。
7.根据权利要求(1)和(6),所述光引发剂和辐射固化配方体系,即光固化涂料或油墨材料,配合各种不同的施工方式(喷涂,滚涂,淋涂,擦涂,浸涂等)和/或施工工序(腻子,底涂,上色,中涂,面涂等),在PCB油墨,激光直接成像(LDI)油墨,印刷包装油墨,木器家具,塑胶产品,印刷包装,喷墨打印,电子消费品,机动车辆内外饰,管道型材,工业地坪,建筑幕墙,3D打印增材制作,以及船舶或集装箱体等下游市场的应用。
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