WO2018090354A1 - 一种无苯释放的光固化组合物 - Google Patents

一种无苯释放的光固化组合物 Download PDF

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WO2018090354A1
WO2018090354A1 PCT/CN2016/106546 CN2016106546W WO2018090354A1 WO 2018090354 A1 WO2018090354 A1 WO 2018090354A1 CN 2016106546 W CN2016106546 W CN 2016106546W WO 2018090354 A1 WO2018090354 A1 WO 2018090354A1
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photocurable composition
acrylate
composition according
compound
alkyl
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PCT/CN2016/106546
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English (en)
French (fr)
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赵文超
王辰龙
闫庆金
麻忠利
王永林
胡伟静
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北京英力科技发展有限公司
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Priority to PCT/CN2016/106546 priority Critical patent/WO2018090354A1/zh
Publication of WO2018090354A1 publication Critical patent/WO2018090354A1/zh

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins

Definitions

  • the present invention relates to a photocurable composition that meets the printing requirements of cigarette wrappers, and more particularly to a photocurable composition that meets the benzene release index.
  • UV curing technology As a new type of green technology, UV curing technology has a wide range of applications in coatings, adhesives, printing inks, photolithography, paper glazing and biomaterials, showing good development prospects.
  • Ultraviolet curing systems generally include the following three main components: prepolymers, monomers, and photoinitiators.
  • Photoinitiators are a key component of this system, and it is directly related to the rapid conversion of oligomers and monomers from liquid to solid in the formulation system. And the photoinitiator is required to have a good curing rate, good surface curing activity, low odor, low yellowing and good solubility. In addition, as consumers become more sensitive to chemical contamination in foods and comply with relevant food processing laws that may be developed and refined in the future, the photoinitiator's mobility and tendency to be captured are as small as possible after the curing process is completed. .
  • benzophenone has become one of the most widely used photoinitiators due to its low price, good surface curing properties, and difficulty in yellowing.
  • benzophenone has certain disadvantages at the same time, its own molecular weight is small, which is easy to volatilize and migrate, resulting in odor and toxicity of the product; and the release of benzene in the process of benzophenone is used, so that its use is affected.
  • the latest tobacco packaging volatiles standard strictly limits the amount of benzene released to a maximum of 0.02 mg/m 2 .
  • a variety of small molecule photoinitiators such as benzophenone, methylbenzophenone, and 4-phenylbenzophenone are included in the banned list.
  • the invention provides a photocurable composition without benzene release and without 4-phenylbenzophenone detection, the composition comprising:
  • n 1, 2, 3;
  • R 1 to R 9 are each independently a hydrogen atom, a chlorine atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, or a phenyl group.
  • the ethylenically unsaturated compound of component a may be an acrylate compound selected from the group consisting of acrylates of monohydric alcohols such as butyl acrylate; or acrylates of polyhydric alcohols such as neopentyl glycol diacrylate, ethoxylated trishydroxyl Methylpropane triacrylate; or an acrylate prepolymer compound such as epoxy acrylate, polyester acrylate, polyether acrylate.
  • Component b represents from 0.1 to 10% of the total mass of the composition.
  • the photocurable composition further comprises component c: an organic tertiary amine selected from the group consisting of isooctyl N,N-dimethylaminobenzoate, Omnipol ASA (IGM) triethanolamine, N-methyldiethanolamine, trialkylamine An adduct of a dialkylamine and a polyol acrylate monomer such as Photomer 4775, Photomer 4250 (IGM), wherein the alkyl group is a C 1 -C 4 alkyl group.
  • an organic tertiary amine selected from the group consisting of isooctyl N,N-dimethylaminobenzoate, Omnipol ASA (IGM) triethanolamine, N-methyldiethanolamine, trialkylamine
  • An adduct of a dialkylamine and a polyol acrylate monomer such as Photomer 4775, Photomer 4250 (IGM), wherein the alkyl group is a C 1 -C 4 alkyl group
  • the photocurable composition further optionally contains component d: an additive, including a pigment, a matting agent, an antifoaming agent, and the necessary ingredients and amounts are added depending on the properties of the composition.
  • an additive including a pigment, a matting agent, an antifoaming agent, and the necessary ingredients and amounts are added depending on the properties of the composition.
  • the photocurable composition is used as a coating or ink, and after they are applied to a substrate, the wet film is cured by irradiation with a high pressure mercury lamp or LED lamp containing a 200 nm to 400 nm emission wave, thereby being manufactured.
  • a high pressure mercury lamp or LED lamp containing a 200 nm to 400 nm emission wave thereby being manufactured.
  • Printing of the above-mentioned photocurable composition can be applied to various substrates such as paper, wood, plastic, metal, and glass, and is particularly suitable for printing on cigarette wrappers.
  • composition of the present invention not only has good reactivity, good surface curability, but also has the characteristics of no benzene release and no detection of 4-phenylbenzophenone.
  • photoinitiators b1, b2, b3, b4, 4-phenyl-3'-methylbenzophenone, benzophenone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

一种无苯释放的光固化组合物，含有组分:a：至少一种乙烯基不饱和化合物，例如丙烯酸酯类化合物；b：式 (I) 结构式化合物之一或两种以上混合物；C:有机三级胺；其中m＝1,2；R为氢原子、C1-C4烷基、(式II) n＝1，2,3；R1-R9各自独立地是氢原子、氯原子、C1-C4烷基、C1-C4烷氧基、苯基。具有无苯释放、无4-苯基二苯甲酮检出的技术效果，适合用于香烟包装纸的印刷。

Description

一种无苯释放的光固化组合物 技术领域：
本发明涉及一种符合香烟包装纸印刷要求的光固化组合物，具体是指符合苯释放指标的光固化组合物。
背景技术：
紫外光固化技术作为一种新型的绿色技术，在涂料、粘合剂、印刷油墨、光刻蚀、纸张上光和生物材料等方面有着广泛的应用，显示着良好的发展前景。紫外光固化体系一般包括以下三种主要组分：预聚体、单体和光引发剂。
光引发剂是该体系的关键组成部分，它直接关系到配方体系在光照射时低聚物及单体能否迅速由液态转变成固态。并且光引发剂要求具备良好的固化速率，良好的表面固化活性，低臭，低黄变和良好的溶解性等特点。此外，随着消费者对食品中化学污染的日益敏感和对未来可能制定和完善的相关食品加工法的遵守，光引发剂在固化过程完成后，其迁移率和被夺取的倾向也尽可能小。
在已经成功应用于生产的众多光引发剂中，二苯甲酮由于其低廉的价格，良好的表面固化性能、不易黄变等优点，成为使用最广的光引发剂之一。但二苯甲酮同时存在着一定的缺点，自身分子量较小，从而容易挥发和发生迁移，导致产品出现气味和毒性；并且二苯甲酮使用过程中有易挥发的苯释放，使其使用受到一定的限制，最新的烟草包装物挥发份标准严格规定了的苯释放量最高限制为0.02mg/m2。同时，将多种小分子光引发剂例如二苯甲酮、甲基二苯甲酮、4-苯基二苯甲酮列入禁止使用清单。
因此，为解决上述问题，开发性能良好、不含禁用物质的光固化组合物 成为该行业的技术研究焦点。
发明内容：
本发明提供一种无苯释放、无4-苯基二苯甲酮检出的光固化组合物，该组合物含有：
a：至少一种乙烯基不饱和化合物；
b：式(Ⅰ)结构式化合物之一或两种以上混合物；
C:有机三级胺；
Figure PCTCN2016106546-appb-000001
其中m＝1,2；R为氢原子、C1-C4烷基、
Figure PCTCN2016106546-appb-000002
n＝1，2,3；
R1-R9各自独立地是氢原子、氯原子、C1-C4烷基、C1-C4烷氧基、苯基。
组分a的乙烯基不饱和化合物可以是丙烯酸酯类化合物，它选自一元醇的丙烯酸酯例如丙烯酸丁酯；或多元醇的丙烯酸酯例如新戊二醇二丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯；或丙烯酸酯类预聚体化合物例如环氧丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯。
作为组分b的式(Ⅰ)化合物的具体结构有b1-b11：
表1
Figure PCTCN2016106546-appb-000003
组分b在组合物总质量中占0.1—10％。
光固化组合物还含有组分c：有机三级胺，选自N,N-二甲氨基苯甲酸异辛酯、Omnipol ASA(IGM公司)三乙醇胺、N-甲基二乙醇胺、三烷基胺、二烷基胺与多元醇丙烯酸酯单体的加成物如Photomer4775、Photomer 4250(IGM公司)，其中烷基为C1-C4烷基。
光固化组合物进一步任意含有组分d：添加剂，包括颜料、消光剂、消泡剂，视组合物的性能需要添加必要的成分和用量。
光固化组合物用作涂料或油墨，当它们被涂布于基材后，使用含有200nm-400nm发射波的高压汞灯或LED灯照射使湿膜固化，由此可以制造 一种在基材上成膜或形成印刷图案的物品。
各种基材例如：纸张、木材、塑料、金属、玻璃上都可以适用上述光固化组合物的印刷，尤其适用于香烟包装纸的印刷。
发明效果
本发明的组合物不仅具有良好的反应活性、良好的表面固化性，还具有无苯释放、无4-苯基二苯甲酮检出的特点。
具体实施例
实施例1-4及对照例1-2：
Figure PCTCN2016106546-appb-000004
*光引发剂共有六种：b1、b2、b3、b4、4-苯基-3’-甲基二苯甲酮、二苯甲酮。
工作条件：
避光条件下，在装有搅拌器的玻璃容器内加入a1)Photomer331647.9g，a2)Photomer 407240g，b)光引发剂4g，c)Photomer4775 8g，d)BYK3070.1g，避光搅拌均匀后，即得到光固化组合物。将该混合物用丝网印刷机在白卡纸板上涂膜，膜的厚度为25um，六种样板以10m/min的速度经过2000W功率的高压汞灯照射，分别得到固化良好的纸上固化膜。按标准YQ69-2015用顶 空-GC分析苯含量；用GC-MS分析二苯甲酮和4-苯基二苯甲酮，计算数据结果在表2。
表2
Figure PCTCN2016106546-appb-000005
在实施例1-4的固化膜中三种限定物质都未检出，而对照例1检出了4-苯基二苯甲酮含量超出标准限定值；对照例2检出了苯和二苯甲酮两种限定物质且大大超出标准限定值。

Claims (11)

  1. 一种无苯释放的光固化组合物，含有组分:
    a：至少一种乙烯基不饱和化合物；
    b：式(Ⅰ)结构式化合物之一或两种以上混合物；
    C:有机三级胺；
    Figure PCTCN2016106546-appb-100001
    其中m＝1，2；R为氢原子、C1-C4烷基、
    Figure PCTCN2016106546-appb-100002
    n＝1，2，3；
    R1-R9各自独立地是氢原子、氯原子、C1-C4烷基、C1-C4烷氧基、苯基。
  2. 根据权利要求1所述的光固化组合物，其中a:至少一种乙烯基不饱和化合物为丙烯酸酯类化合物，选自一元醇的丙烯酸酯、多元醇的丙烯酸酯或丙烯酸酯类预聚体化合物。
  3. 根据权利要求2所述的光固化组合物，其中，a中的丙烯酸酯类预聚体化合物为环氧丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯。
  4. 根据权利要求1所述的光固化组合物，其中,式(Ⅰ)结构式化合物的具体结构为：
    Figure PCTCN2016106546-appb-100003
    Figure PCTCN2016106546-appb-100004
  5. 根据权利要求1所述的光固化组合物，其中，组分b的含量为0.1—10％。
  6. 根据权利要求1所述的光固化组合物，其中，组分c：有机三级胺包括N,N-二甲氨基苯甲酸异辛酯、聚乙二醇二(N,N-二甲氨基苯甲酸)酯、三乙醇胺、N-甲基二乙醇胺、三烷基胺、二烷基胺与多元醇丙烯酸酯单体的加成物，其中烷基为C1-C4烷基。
  7. 根据权利要求1所述的光固化组合物，进一步含有添加剂，添加剂包括颜料、消光剂、消泡剂中的一种或多种。
  8. 根据权利要求1-7所述的光固化组合物，用作涂料或油墨。
  9. 根据权利要求1-7所述的光固化组合物，被涂布于基材后，使用含有200nm-400nm发射波的高压汞灯照射产生固化。
  10. 根据权利要求1-7所述的光固化组合物，进一步根据权利要求8的应用和权利要求9的固化所制造的一种物品。
  11. 根据权利要求10，一种物品是香烟包装纸。
PCT/CN2016/106546 2016-11-21 2016-11-21 一种无苯释放的光固化组合物 WO2018090354A1 (zh)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1504448A (zh) * 2002-11-28 2004-06-16 北京英力科技发展有限公司 带活性侧链的酮类光引发剂化合物及其制备方法和应用
CN101172951A (zh) * 2006-11-02 2008-05-07 北京英力科技发展有限公司 羟基乙氧基二苯甲酮羧酸酯及其作为光引发剂的用途
CN104797671A (zh) * 2012-11-19 2015-07-22 3M创新有限公司 高度增粘丙烯酸酯压敏粘合剂
CN105601825A (zh) * 2015-12-24 2016-05-25 江苏苏博特新材料股份有限公司 一种具有较高黏土忍耐性的减水剂的制备方法
JP2016164222A (ja) * 2015-03-06 2016-09-08 スリーエム イノベイティブ プロパティズ カンパニー 紫外線架橋性組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1504448A (zh) * 2002-11-28 2004-06-16 北京英力科技发展有限公司 带活性侧链的酮类光引发剂化合物及其制备方法和应用
CN101172951A (zh) * 2006-11-02 2008-05-07 北京英力科技发展有限公司 羟基乙氧基二苯甲酮羧酸酯及其作为光引发剂的用途
CN104797671A (zh) * 2012-11-19 2015-07-22 3M创新有限公司 高度增粘丙烯酸酯压敏粘合剂
JP2016164222A (ja) * 2015-03-06 2016-09-08 スリーエム イノベイティブ プロパティズ カンパニー 紫外線架橋性組成物
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CN105601825A (zh) * 2015-12-24 2016-05-25 江苏苏博特新材料股份有限公司 一种具有较高黏土忍耐性的减水剂的制备方法

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