CN103703030A - 一种低迁移性光引发剂 - Google Patents
一种低迁移性光引发剂 Download PDFInfo
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- CN103703030A CN103703030A CN201380000868.5A CN201380000868A CN103703030A CN 103703030 A CN103703030 A CN 103703030A CN 201380000868 A CN201380000868 A CN 201380000868A CN 103703030 A CN103703030 A CN 103703030A
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- 239000012046 mixed solvent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
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Abstract
本发明提供一种式(Ⅰ)所示的光引发剂,其中PI是一种能够在暴露于光化辐射时引发自由基聚合反应的含芳环的光引发剂基团,通过芳环与Y相连;Y为CH2、CO、C(O)CH2O、C(O)CH2S、C(O)CH2CH2S,且以基团右端与PI相连;G为丙烯酸酯或多元醇丙烯酸酯除烯键之外的残基;R为C1-C12烷基、被O、S、NR’隔断的C4-C12烷基;R’为C1-C12烷基、苯基;n=1-6的整数;m=1-6,且小于等于n的整数;p=0-4,且小于m的整数。本发明还提供一种包含(Ⅰ)所示光引发剂的光固化组合物,式(Ⅰ)作为光引发剂使用具有极低迁移性的特点。
Description
技术领域
本发明涉及一种新型的低迁移性光引发剂,用于各种涂料组合物。本发明还提供至少一种以本发明所述化合物作为光引发剂的光固化组合物。
背景技术
光固化技术作为一种新型、先进的材料表面处理技术,自二十世纪六十年代实现产业化以来取得了快速发展,特别是它的高效、优质、环保、节能等特性,使光固化产品的应用日益广泛。光引发剂是光固化材料的关键组分,对材料的光固化速度起决定性作用。采用传统的小分子光引发剂时,在光固化材料涂层固化后,光引发剂的一部分接受光能分解成自由基发挥聚合引发作用并在聚合终止时与其他自由基结合,要么接在聚合物链上,要么以更小分子量的碎片形式与剩余没分解的光引发剂残留在聚合网络中,随着时间推移逐渐向涂层表面迁移,影响涂层外观和性能并使涂层黄变,甚至产生毒理作用,影响其在食品和卫生包装材料上的使用。为了克服小分子光引发剂的上述不足,人们设计了大分子光引发剂或可聚合的光引发剂,大分子光引发剂是将光引发剂以碳原子或氧原子连接到高分子或低聚物的链上,目前已经商品化的大分子光引发剂为意大利宁柏迪以KIP150为主的KIP系列和KT系列产品、英国Lambson公司的Speedcure系列产品以及中国专利CN1599713公开的以聚醚多元醇为核心的二苯甲酮氧乙酸酯系列;CN101434534公开了以脂肪二醇为核心的二苯甲酮氧乙酸酯;CN101153037公开了羟基乙氧基二苯甲酮羧酸酯的制备;ZL200710090821.9公开了苯基二苯甲酮的大分子化;中国专利CN1887913公开了聚氨酯型链接二苯甲酮的制备;可聚合的光引发剂是在光引发剂结构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4-羟基二苯甲酮的丙烯酸酯或甲基丙烯酸酯。具体如CN103113498公开的一种同时含有二苯甲酮及三级胺及不饱和双键的可聚合光引发剂;CN103044582公开的一种含吖啶酮的可聚合光引发剂。
发明内容
本发明的目的是提供一种新型的低迁移性光引发剂。并提供一种含有这种新型低迁移性光引发剂的光固化组合物,该光固化组合物用于光固化涂料、黏合剂、油墨配方中,由于引发剂基团被有效链接在聚合物链段上或者其本身就具有足够大的分子量,同时,分子中的酰胺键或醚键具有良好的稳定性,所以该光引发剂具有极低迁移率的特点。
本发明所提供的低迁移性光引发剂为结构式Ⅰ所示化合物:
其中PI是一种能够在暴露于光化辐射时引发自由基聚合反应的含芳环的光引发剂基团,通过芳环与Y相连;
Y为CH2、CO、C(O)CH2O、C(O)CH2S、C(O)CH2CH2S,且以基团右端与PI相连;
G为丙烯酸酯或多元醇丙烯酸酯除烯键之外的残基;
R为C1-C12烷基、被O、S、NR’隔断的C4-C12烷基;
R’为C1-C12烷基、苯基;
n=1-6的整数;m=1-6,且小于等于n的整数;p=0-4,且小于m的整数。
上述通式Ⅰ所示的光引发剂化合物,PI是取代或不被取代的二苯甲酮基、取代或不被取代的噻吨酮基、取代或不被取代的咔唑基;Y为CO、C(O)OCH2、C(O)CH2S、C(O)CH2CH2S;G为二元和二元以上多元醇丙烯酸酯除烯键之外的残基;R为C1-C12烷基;n=2-6的整数;m=2-6,且小于等于n的整数;p=0-4,且小于m的整数。
PI光引发剂基团可以优选下述结构:
Y-PI的优选的例子有:
G的具体例子有
R的具体例子有丁基,辛基。
这些化合物作为光引发剂应用在紫外光固化组合物中。
本发明还提供一种光固化组合物,其中包括:
(a)至少一种结构式Ⅰ所示的化合物,与
(b)至少一种可进行自由基聚合的碳碳双键式不饱和化合物。
所述的光固化组合物中,组分(a)占所述组合物总重量的1-50%。
组分(b)所述的可进行自由基聚合的碳碳双键式不饱和化合物可以包括一个或多个不饱和碳碳双键,这些化合物可以是低分子量的(单体)或者高分子量的(低聚物)。包含一个双键的单体的例子为烷基或羟烷基的丙烯酸酯或甲基丙烯酸酯,例如丙烯酸甲酯,丙烯酸乙酯等。另外也可以使用硅氧烷丙烯酸酯,丙烯腈,丙烯酰胺,乙烯基醚如异丁基乙烯基醚,苯乙烯,烷基苯乙烯,N‐乙烯吡咯烷酮,氯乙烯。
包含两个或者多个双键的例子有乙二醇及其聚醚二醇,丙二醇及其聚醚二醇,新戊二醇,己二醇或者双酚A的二丙烯酸酯或二(甲基丙烯酸酯)等。
相对高分子量的多不饱和化合物(低聚物)的例子为丙烯酸化的环氧树脂,丙烯酸化的聚酯,包含乙烯基醚或环氧基团的聚酯,以及还有聚氨酯和聚醚。不饱和低聚物另外的例子为不饱和聚酯树脂,所述树脂通过由马来酸,邻苯二甲酸和一种或多种二元醇制得,并且其分子量500‐3000。此外,还能使用乙烯基醚单体或者其低聚物,并且还能使用带有聚酯、聚氨酯、聚醚、聚乙烯醚和环氧主链的马来酸酯封端的低聚物。
特别合适的例子为双键不饱和羧酸和多元醇或聚环氧化物的酯,和在主链或侧链中有双键不饱和基团的聚合物,例如,不饱和聚酯,聚酰胺和聚氨酯及其共聚物,在侧链中包含(甲基)丙烯酸基团的聚合物和共聚物,以及含有一种或多种所述聚合物的混合物。其中不饱和羧酸的例子为丙烯酸,甲基丙烯酸,巴豆酸,衣康酸,肉桂酸,以及不饱和脂肪酸,如亚麻酸或油酸。优选丙烯酸,甲基丙烯酸。合适的多元醇为脂族和脂环族多元醇或带有羟基端基的低聚酯类。
脂族和脂环族多元醇的例子为优选带有2‐12碳原子的亚烷基二醇如乙二醇,1,2‐或1,3‐丙二醇,1,2‐、1,3‐或1,4‐丁二醇,戊二醇,己二醇,辛二醇,十二烷二醇,二甘醇,三甘醇,分子量优选从200‐1500的聚乙二醇,1,3‐环戊二醇,1,2‐、1,3‐或1,4‐环己二醇,1,4‐二羟基甲基环己烷,甘油,三(β羟基乙基)胺,三羟基甲基乙烷,三羟甲基丙烷,季戊四醇,二季戊四醇和山梨醇。
可以单独地或者以任何希望的混合物的形式使用上述的可进行自由基聚合的烯键式不饱和化合物,优选丙烯酸酯类化合物、乙烯基醚类化合物或其混合物。
除结构式Ⅰ化合物之外,在上述光固化组合物中还可以含有其他类型的已知光引发剂的一种或两种以上混合物,已知的光引发剂有二苯甲酮、2-异丙基硫杂蒽酮、2-羟基-2-甲基-苯基-1-丙酮、1-羟基环己基苯基甲酮、2-甲基-2-(4-吗啉基)-(4-甲硫基)苯基-1-丙酮、2,4,6-三甲基苯甲酰基二苯基氧化膦等。
所述的光固化组合物中,可以加入胺类化合物作为助剂,例如三级胺类化合物,如三乙胺、三乙醇胺,二甲氨基苯甲酸乙酯,或活性胺类化合物,如二乙胺与乙氧基化三羟甲基丙烷三丙烯酸酯加成物。胺类化合物用量是组合物总重量的0.05‐15%。
所述的光固化组合物中,还可以根据应用领域和该领域所需的性能,添加各种助剂,如:在有色体系(色漆、油墨等)中,需要加入颜料,例如:二氧化钛、酞青蓝等;为了达到良好的流动平整性,需要加入流平剂;为了抑制体系中气泡的形成,往往加入消泡剂;消光剂的加入则是为了降低固化膜的光泽,得到低光泽或亚光涂料,各种添加剂在各领域的添加量也是常用量。
本发明还提供一种固化上述光固化组合物的方法,即将上述光固化组合物涂布成薄膜状,用紫外线照射使膜固化。紫外线光源来自发射紫外线光(UV)的设备,按需要发射足够强度的光谱范围230‐450nm的光线照射在涂布过的本发明光固化组合物上,就能引发聚合,得到固化膜。
本发明还提供一种上述光固化组合物的用途,用于制造光固化罩光清漆,印刷油墨,粉末涂料,印版,粘合剂,牙科用组合物,光学波导管,颜色涂胶体系,玻纤电缆涂层,电子线路板,借助立体印刷生产的三维物体,图像记录材料。
本发明还提供一种结构式Ⅰ化合物的合成方法:
(1)将结构式Ⅱ所示丙烯酸酯类化合物与式Ⅲ所示的伯胺进行加成得到中间体结构式Ⅳ化合物,
其中,G,R,n,m如上所述。
反应在正常情况下优选在伴有溶剂的状况下进行,溶剂的性质对于本发明来说并非关键之所在,只要它对试剂或反应无不良影响即可。适合的溶剂包括:芳烃,卤代烃,例如苯、甲苯、二氯甲烷或二氯乙烷。
反应在常温或低温进行,可以不经后处理直接进行下一步反应。
(2)将结构式Ⅳ化合物和结构式Ⅴ化合物进行酰胺化反应,可得本发明化合物。
其中,G,R,n,m、p、PI定义同前述结构式Ⅰ中所定义,Y为CO、COCH2O、COCH2S、COCH2CH2S。
具体方法为:将结构式Ⅴ化合物加入上一步的反应液中,再加入碱如三乙胺等,常温或低温反应,反应完毕,反应液经碱洗,脱溶得到产品。
(3)将结构式Ⅳ化合物和结构式Ⅴ化合物进行胺化反应,可得本发明化合物。
反应式同上面(2)中反应式,其中,G,R,n,m、p、PI定义同前述结构式Ⅰ中所定义,Y为CH2。
具体方法为:将结构式Ⅴ化合物加入上一步的反应液中,再加入碱如三乙胺等,常温或低温反应,反应完毕,反应液经碱洗,脱溶得到产品。
本发明所述的光引发剂易于制备,应用到光固化组合物中,该光固化组合物完全光固化所需要的固化次数少,光固化效率较高;光固化后,成膜的气味小;在迁移率方面表现尤为突出,实现极低迁移性。
具体实施例
实施例1
在100ml三口瓶中,加入11g(0.15摩尔)正丁胺,50ml二氯乙烷,向三口瓶中滴加11.3g(0.05摩尔)1,6-己二醇二丙烯酸酯(HDDA),常温反应4h。反应液用水洗2次,每次30ml,二氯乙烷相脱溶得到17.1g无色液体,收率92%。
在100ml三口瓶中,加入上步反应得到的HDDA加成产物7.5g(0.02摩尔),50ml二氯乙烷,11g(0.04摩尔)4-苯甲酰基苯氧乙酰氯,4.1g(0.04摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液加入5%氢氧化钠溶液,搅拌15min,过滤。分液,二氯乙烷相用水洗2次,每次30ml,二氯乙烷相减压蒸馏,得到14.1g结构式Ⅵ化合物,为淡黄色油状物,收率83%,产物的核磁氢谱鉴定结果如下:
1H-NMR(300HMz,CDCl3):δH(ppm)0.93(t,6H,CH3),1.37(m,8H,CH2),1.62(m,8H,CH2),2.63(t,4H,CH2CO),3.36(t,4H,CH2N),3.61(t,4H,CH2N),4.06(t,4H,OCH2),4.79(s,4H,OCH2CO),7.00(dd,4H,ArH),7.47(m,6H,ArH),7.80(m,8H,ArH)。
实施例2
在100ml三口瓶中,加入11.3g(0.05摩尔)1,6-己二醇二丙烯酸酯(HDDA),40ml二氯乙烷,向三口瓶中滴加3.7g(0.05摩尔)正丁胺,常温反应4h。
然后在该反应体系中加入14.7g(0.05摩尔)4-苯甲酰基苯氧乙酰氯,5.0g(0.05摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液加入5%氢氧化钠溶液30ml,搅拌15min,过滤。分液,二氯乙烷相用水洗2次,每次30ml,二氯乙烷相脱溶,得到20.8g淡黄色油状产物,其中结构式Ⅶ占57%,结构式Ⅵ占29%。
实施例3
在100ml三口瓶中,加入HDDA与正丁胺的加成产物7.5g(0.02摩尔)(制备见实施例1),40ml二氯乙烷,12.2g(0.04摩尔)硫杂蒽酮-2-氧代乙酰氯,4.1g(0.04摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液用3cm厚硅胶(200-300目)过滤,滤液用水洗2次,每次30ml,二氯乙烷相脱溶,得到11.1g结构式Ⅷ产物,淡黄色固体,收率61%。产物的核磁氢谱鉴定结果如下:
1H-NMR(300HMz,CDCl3):δH(ppm)0.93(t,6H,CH3),1.34(m,8H,CH2),1.62(m,8H,CH2),2.66(t,4H,CH2CO),3.36(t,4H,CH2N),3.63(t,4H,CH2N),4.06(t,4H,OCH2),4.82(s,4H,OCH2CO),7.36(s,2H,ArH),7.50(m,4H,ArH),7.59(m,4H,ArH),8.0(d,2H,ArH),8.59(d,2H,ArH)
实施例4
在100ml三口瓶中,加入4.5g(0.02摩尔)1,6-己二醇二丙烯酸酯(HDDA),30ml二氯乙烷,向三口瓶中滴加1.5g(0.02摩尔)正丁胺,常温反应4h。加入6.1g(0.02摩尔)硫杂蒽酮-2-氧代乙酰氯,2.0g(0.02摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液用3cm厚硅胶(200-300目)过滤,滤液用水洗2次,每次30ml,二氯乙烷相脱溶,得到6.5g红棕色油状产物,其中结构式Ⅸ占60.2%,结构式Ⅷ占29.6%,具体HPLC-MS分析结果见表1。
表1实施例4产物液相色谱―质谱联用分析结果
实施例5
在100ml三口瓶中,加入7.3g(0.1摩尔)正丁胺,30ml二氯乙烷,滴加2.6g(0.02摩尔)丙烯酸丁酯,室温反应4h。反应液用水洗2次,每次30ml,二氯乙烷相脱溶得3.4g无色液体。
向上述加成产物中加入20ml二氯乙烷,1.7g(0.017摩尔)三乙胺,4.7g(0.017摩尔)4-苯甲酰基苯氧乙酰氯,水浴20-30℃下搅拌2h。反应液加入5%氢氧化钠溶液,搅拌15min,过滤。分液,二氯乙烷相用水洗2次,每次30ml,二氯乙烷相减压蒸馏,得到6.2g结构式Ⅹ化合物,为淡黄色油状物,收率83%,产物的核磁氢谱鉴定结果如下:
1H-NMR(300HMz,CDCl3):δH(ppm)0.92(6H,CH3),1.35(m,4H,CH2),1.59(m,4H,CH2),2.64(t,2H,CH2CO),3.33(t,2H,CH2N),3.64(t,2H,CH2N),4.09(t,2H,OCH2),4.77(s,2H,OCH2CO),7.00(t,2H,ArH),7.49(t,2H,ArH),7.55(t,1H,ArH),7.74(d,2H,ArH),7.81(d,2H,ArH)
实施例6
在100ml三口瓶中,加入3.0g(0.01摩尔)三羟甲基丙烷三丙烯酸脂,30ml二氯乙烷,向三口瓶中滴加2.6g(0.02摩尔)正辛胺,常温反应5h。加入5.5g(0.02摩尔)(4-苯甲酰基)苯氧乙酰氯,2.1g(0.02摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液加入5%氢氧化钠溶液,搅拌15min,过滤。分液,二氯乙烷相用水洗2次,每次30ml,二氯乙烷相减压蒸馏,得8.6g结构式Ⅺ化合物,为淡黄色粘稠状物。
实施例7
(1)在500ml三口瓶中加入4‐氯二苯甲酮55g与巯基乙酸24g,用DMF350ml溶解,加入固体氢氧化钠23g,升温回流(105‐110℃),HPLC检测4‐氯二苯甲酮含量小于1%时开始降温,将反应液加入500ml水中,用100ml甲苯萃取水不溶物。用浓盐酸调水相pH值至3‐4,有固体析出,过滤得粗品,烘干得58g;二氯乙烷重结晶,得白色结晶4‐(羧甲基硫基)二苯甲酮52g,收率75%。熔点133‐134℃。
(2)将4-(羧甲基硫基)二苯甲酮27g(0.1摩尔)加入100ml二氯乙烷中,加入14g(0.12摩尔)亚硫酰氯,加热至回流(80-85℃),HPLC检测4-(羧甲基硫基)二苯甲酮含量小于1%时开始降温,反应液脱溶得4-苯甲酰基苯硫基乙酰氯。
(3)在100ml三口瓶中,加入11.3g(0.05摩尔)1,6-己二醇二丙烯酸酯(HDDA),40ml二氯乙烷,向三口瓶中滴加3.7g(0.05摩尔)正丁胺,常温反应4h。
反应体系中,再加入14.5g(0.05摩尔)4-苯甲酰基苯硫基乙酰氯,5.0g(0.05摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液加入5%氢氧化钠溶液30ml,搅拌15min,过滤。分液,二氯乙烷相用水洗2次,每次30ml,二氯乙烷相脱溶,得到结构式Ⅻ化合物22.6g,为淡黄色油状物。
实施例8
(1)将15.4g(0.1摩尔)联苯14.6g(0.11摩尔)无水三氯化铝溶于60ml二氯乙烷,滴加19.3g(0.11摩尔)对氯苯甲酰氯,20℃左右搅拌反应4小时,将反应液投入200ml10%盐酸溶液中,水洗至pH值5‐6,浓缩回收二氯乙烷得4’‐氯‐4‐苯基二苯甲酮。经1:5(重量比)的乙酸乙酯‐石油醚混合溶剂重结晶得到纯度为98.1%的白色固体粉末,重量26.4g,收率91%。熔点169.1‐171.2℃。
(2)4’‐(羧甲基硫基)‐4‐苯基二苯甲酮的制备
在500ml三口瓶中加入4’‐氯‐4‐苯基二苯甲酮14.6g(0.05摩尔)与巯基乙酸5.5g(0.06摩尔),用DMF80ml溶解,加入固体氢氧化钠6.0g(0.15摩尔),升温回流(105‐110℃),HPLC检测4’‐(羧甲基硫基)‐4‐苯基二苯甲酮含量小于1%时开始降温,将反应液加入500ml水中,用100ml甲苯萃取水不溶物。用浓盐酸调水相pH值至3‐4,有固体析出,过滤得粗品,烘干得17.6g;二氯乙烷重结晶,得白色结晶13.2g,收率76%。
(3)4’‐(羧甲基硫基)‐4‐苯基二苯甲酮10.4g(0.03摩尔)加入60ml二氯乙烷中,加入4.7g(0.04摩尔)亚硫酰氯,加热至回流(80‐85℃),HPLC检测4’‐(羧甲基硫基)‐4‐苯基二苯甲酮含量小于1%时开始降温,反应液脱溶得4‐(4‐苯基)苯甲酰基苯硫基乙酰氯。
(4)在100ml三口瓶中,加入4.5g(0.02摩尔)1,6-己二醇二丙烯酸酯(HDDA),30ml二氯乙烷,向三口瓶中滴加1.5g(0.02摩尔)正丁胺,常温反应4h。加入7.3g(0.02摩尔)4-(4-苯基)苯甲酰基苯硫基乙酰氯,2.0g(0.02摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液加入5%氢氧化钠溶液30ml,搅拌15min,过滤。分液,二氯乙烷相用水洗2次,每次30ml,二氯乙烷相脱溶,得到11.5g结构式ⅩⅢ产品,为黄色粘稠物。
实施例9
在100ml三口瓶中,加入12.8gEO3-TMPTA,30ml二氯乙烷,向三口瓶中滴加4.4g(0.06摩尔)正丁胺,常温反应4h。
反应体系中再加入18.5g(0.06摩尔)硫杂蒽酮-2-氧代乙酰氯,6.0g(0.06摩尔)三乙胺,水浴20-30℃下搅拌2h。反应液用3cm厚硅胶(200-300目)过滤,滤液用水洗2次,每次30ml,二氯乙烷相脱溶,得到22.8g结构式ⅩⅣ化合物,为红棕色粘稠状物。
实施例10实施例2产物的应用评价
实施例2的产物6.0g与其它组分按表2数量配制成光固化组合物。放置48小时后使用。
表2
组分 | 质量g | 百分比例% | 供应商 |
621A-80 | 12 | 24 | 台湾长兴工业品 |
EO3-TMPTA | 30 | 60 | 天津天骄工业品 |
实施例2产物 | 6.0 | 12 | 本发明实验样品 |
将配制所得的透明组合物用15微米线棒涂布器施印到10×10cm马口铁板和12×12纸板上,用一台功率为80瓦/厘米中压水银弧光灯以20米/分的速度进行固化。纪录获得良好的表面及彻底固化所需要的灯下通过次数。人工评估在马口铁板上的固化膜气味,气味最大为5级,最小为1级。将纸板剪裁为10×10cm大小,完全浸入100mL蒸馏水、3%醋酸水溶液两种模拟液中,密封好在40℃条件下放置10天。取出印刷物,静置后直接进行HPLC分析模拟液中4-苯甲酰基苯氧基乙酸含量。使用欧盟模型,假定600cm2印刷面积包装1kg食品,迁移率测量结果以ppb或μg/Kg食品表示,其结果如表5所示。
实施例11:实施例4产物的应用
实施例4的产物6.0g与其它组分按表3数量配制成光固化组合物。放置48小时后使用。
表3
组分 | 质量g | 百分比例% | 供应商 |
621A-80 | 12 | 24 | 台湾长兴工业品 |
EO3-TMPTA | 30 | 60 | 天津天骄工业品 |
实施例4的产物 | 6.0 | 12 | 本发明试验样品 |
将配制所得的透明组合物用15微米线棒涂布器施印到10×10cm马口铁板和12×12纸板上,用一台功率为80瓦/厘米中压水银弧光灯以20米/分的速度进行固化。纪录获得良好的表面及彻底固化所需要的灯下通过次数。人工评估在马口铁板上的固化膜气味,气味最大为5级,最小为1级。将纸板剪裁为10×10cm大小,完全浸入100mL蒸馏水、3%醋酸水溶液两种模拟液中,密封好在40℃条件下放置10天。取出印刷物,静置后直接进行HPLC分析模拟液中硫杂蒽酮-2-氧乙酸含量。使用欧盟模型,假定600cm2印刷面积包装1kg食品,迁移率测量结果以ppb或μg/Kg食品表示,其结果如表5所示。
对比实施例1:二苯甲酮作为原料配制光固化组合物
用二苯甲酮代替实施例2产物,实验过程同实施例10,二苯甲酮的检出量非常高,实验结果见表5。
对比实施例2:IHT-PL 2702的应用
用IHT-PL2702(北京英力科技发展有限公司产品)代替二苯甲酮,实验过程同对比实施例1,实验结果见表5。
实施例12:实施例4产物用于配制含黄色颜料光固化组合物
按如下表4配方比例称取各组分,将黄色颜料色浆和树脂621A-80混练均匀,加入实施例4产物,形成黄色光固化组合物。放置48小时后按实施例14的涂布和检测方法得到相应数据,见表5。
表4
组分 | 质量g | 百分比例% | 供应商 |
621A-80 | 12 | 24 | 台湾长兴工业品 |
EO3-TMPTA | 32 | 64 | 天津天骄工业品 |
实施例4产物 | 4.0 | 8 | 本发明试验样品 |
黄3G颜料 | 2.0 | 4 | BASF |
表5性能评价实验结果
*方法检测限0.78
从表5中的性能评价实验结果可以看出,本发明所提供的光引发剂化合物用于光固化组合物,所得到的光固化组合物完全光固化所需要的固化次数少,光固化效率较高;光固化后,成膜的气味小;与小分子光引发剂二苯甲酮和大分子的光引发剂IHT-PL2702比较,在迁移率方面表现尤为突出,实现极低迁移率。
Claims (9)
2.权利要求1的通式Ⅰ所示的光引发剂,其中PI是取代或不被取代的二苯甲酮基、取代或不被取代的噻吨酮基、取代或不被取代的咔唑基。
3.权利要求1的通式Ⅰ所示的光引发剂,其中
Y为CO、COCH2O、COCH2S、COCH2CH2S;
G为二元和二元以上多元醇丙烯酸酯除烯键之外的残基;
R为C1-C12烷基;
n=2-6的整数;m=2-6,且小于等于n的整数;p=0-4,且小于m的整数。
5.一种光固化组合物,含有至少一种权利要求1的通式Ⅰ所示的光引发剂作为组分(a),另含有至少一种可进行自由基聚合的碳碳双键式不饱和化合物作为组分(b)。
6.一种根据权利要求5所述的光固化组合物,其中组分(a)占所述组合物总重量的1-50%。
7.一种根据权利要求5所述的光固化组合物,其中组分(b)包括丙烯酸酯类化合物、乙烯基醚类化合物或其混合物。
8.一种固化光固化组合物的方法,包括将权利要求5的光固化组合物涂布成薄膜状,用紫外线照射使膜固化。
9.一种权利要求5所述的光固化组合物的用途,用于制造光固化罩光清漆,印刷油墨,粉末涂料,粘合剂,牙科用组合物,电子线路板,图像记录材料。
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