WO2011160262A1 - 低挥发性苯甲酰基甲酸酯 - Google Patents

低挥发性苯甲酰基甲酸酯 Download PDF

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WO2011160262A1
WO2011160262A1 PCT/CN2010/000949 CN2010000949W WO2011160262A1 WO 2011160262 A1 WO2011160262 A1 WO 2011160262A1 CN 2010000949 W CN2010000949 W CN 2010000949W WO 2011160262 A1 WO2011160262 A1 WO 2011160262A1
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compounds
compound
component
alkyl
composition
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PCT/CN2010/000949
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French (fr)
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赵文超
王永林
陈东阳
李家齐
张珏
姚丽秀
邵俊峰
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北京英力科技发展有限公司
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Priority to PCT/CN2010/000949 priority Critical patent/WO2011160262A1/zh
Priority to CN201110170943.5A priority patent/CN102442909B/zh
Publication of WO2011160262A1 publication Critical patent/WO2011160262A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/738—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • This application relates to low volatility benzoylformate, either alone as a photoinitiator or in combination with other photoinitiators, for formulating photopolymerizable compositions containing unsaturated carbon-carbon double bond compounds.
  • Phenyl phthalate phthalate has been used as a separate photoinitiator in various compositions in the patent literatures such as U.S. Patent No. 4,038, 164, U.S. Patent No. 4, 475, s, U.S. Pat.
  • U.S. Patent No. 4,038, 164 U.S. Patent No. 4, 475
  • s U.S. Pat.
  • Coatings requiring low odor and low migration are widely used in civilian applications such as paper and flooring.
  • stricter testing standards for food and drug packaging materials limit the amount of material migration, and many small molecular weight substances are excluded from the permitted list.
  • diphenyl fluorenone, 2-hydroxy-2-mercapto-phenyl-1-propanone, benzoyl carboxylic acid decyl ester, ethyl ester and other compounds have small molecular weights, and they may be applied during and after the composition. Contamination of the contact or migration to the air causes contamination.
  • No. 4,507,187 discloses a benzoyl carboxylic acid ester with a siloxane
  • US Pat. No. 3,930, 868 and US Pat. No. 4,038, 394 disclose that a substituted benzoyl carboxylic acid ester having an acrylate group is attached to the resin by double bond polymerization, thereby reducing Volatile.
  • W09833761 discloses diphenyl phthalate ester of ethylene glycol and diethylene glycol as a nonvolatile photoinitiator.
  • the molecular weight of ethylene glycol dibenzoylformate is only 326, diethylene glycol II.
  • the molecular weight of benzoyl phthalate is 370, which is not ideal in terms of heat volatility and can still be perceived.
  • the more obvious odor the measured thermogravimetric analysis showed that 10% loss at 200 °C, 20% weight loss at 250 °C, and 50% loss at 300 °C.
  • the purpose of the present application is to provide a class of low volatility compounds as shown in Structural Formula I.
  • Ri is a hydrogen atom, C "C" alkyl, phenyl or 0R 2 ; ⁇ is -C 4 alkyl, hydroxyethyl;
  • the alkyl group is linear or branched, for example, anthracenyl, ethyl, n-propyl, n-butyl, isopropyl, isobutyl, tert-butyl.
  • the agent is mixed for photopolymerization of unsaturated carbon-carbon double bond compounds.
  • the preparation of the compound of the formula I in the present application is first to synthesize a decyl decanoyl decanoate or a decyl benzoyl decanoate, and then with a dimer or poly 1,4-butanediol or a mixture thereof under the action of a catalyst
  • the catalyst is commonly used in transesterification such as sodium decoxide, sodium ethoxide, dibutyltin oxide or p-toluenesulfonic acid.
  • the treatment of the reaction liquid is usually washing, distillation, and the like which are well known to those skilled in the art.
  • One or a mixture of the compounds of the formula I can be used as a photoinitiator as a composition with at least one compound which can undergo free radical polymerization and which contains an unsaturated carbon-carbon double bond, and photopolymerization can take place.
  • One of the compounds containing an unsaturated carbon-carbon double bond refers to an acrylate of a monohydric or polyhydric alcohol and other structural polyols, such as hexanediol diacrylate, polyester polyol acrylate; secondly, vinyl ether, vinyl Benzene, etc.
  • esters, amides and the like of unsaturated dicarboxylic acids are also esters, amides and the like of unsaturated dicarboxylic acids.
  • one or more mixtures of other types of known photoinitiators and additives which improve the properties of the composition may be included in the composition; known photoinitiators are benzophenone, 2-isopropylthioxanthone, 2-hydroxy-2-indolyl-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 1-mercapto-2-(4-morpholinyl) One (4-indolethio)phenyl-1-propanone 2,4,6-trimercaptobenzoyldiphenylphosphine oxide, etc.; the additive contains a substance as a stabilizer such as p-methoxyphenol, 2-( 2, -Hydroxy-5'-tert-butylphenyl)benzotriazole; a substance as a polymerization accelerator such as triethanolamine or p-nonylaminobenzoate.
  • a pigment By adding a pigment to the composition, an ink of a corresponding color
  • the compound is used in an amount of from 0.1 to 10% by weight based on the total weight of the composition, and the amount of the compound is usually from 1 to 6% to give a good photopolymerization.
  • the prepared composition can be designed to be applied to various substrate surfaces, such as paper, wood, plastic, metal, and coated and irradiated with light in a manner generally used by those skilled in the art to complete the curing process. Both the pre-cured composition and the cured paint film have a very low odor. detailed description
  • diethylene glycol dibenzoyl phthalate is prepared, that is, 164 g of methyl benzoylformate, 16 6 g of diethylene glycol and 10 g of dibutyltin oxide are mixed and heated to 120 "C, and Methanol was distilled off, and finally excess benzoyl decanoate was removed under reduced pressure to obtain a yellow-green liquid, which was analyzed by high pressure liquid chromatography to contain 2% of phenylnonanoyl phthalate, containing diethylene glycol monobenzoyl group.
  • the ester is 20% and contains diethylene glycol bisbenzoylformate 78%.
  • the measured data of the Q5000 thermogravimetric analyzer of the United States Instruments showed that the methyl benzoylcarboxylate (MBF) was at 120. C loss 50%, 140 ° C that is completely volatile; the sample of Comparative Example 1 lost 1.0% at 200 ° C, 25 (TC has 22% weight loss, 300 ° C loss 50 ° /.; and Example 1 The sample lost only 2% at 200 °C, 25 (TC lost only 5% by weight, 30 (20% loss at TC, indicating that the sample of Example 1 has significant heat resistance improvement and very low volatility.
  • the data is shown in Figure 2.
  • the resulting varnish composition was applied to a tinplate using a 10 micron bar coater and cured at a speed of 100 m/min using a 6 watt/cm medium pressure mercury arc lamp. Record the number of passes under the lamp required to obtain a good surface and complete cure. The results are shown in Table 4.
  • the formulated varnish was applied to a tinplate using a ⁇ ⁇ micron bar coater and cured at a speed of 100 m/min with a medium-pressure mercury arc lamp of 0. watt/cm. Record the number of passes under the lamp required to obtain a good surface and complete cure. The maximum odor is 5 and the minimum is 1. The results are shown in Table 4.

Description

低挥发性苯甲酰基甲酸酯
技术领域
本申请涉及低挥发性苯曱酰基甲酸酯， 单独作为光引发剂或与其它光引发剂 混合用于配制含有不饱和碳碳双键类化合物的光致聚合组合物。 背景技术
在专利文献例如 US4038164 , US4475999 , EP132868A1和 GB1534320A1 中已 经将苯曱酰基曱酸酯作为独立的光引发剂在各种组合物中使用， 起到了光致聚 合的作用。 但是， 在光致聚合涂料的实际使用中， 人们注意到小分子量光引发 剂存在的污染问题后， 对低挥发性和低迁移性的光引发剂需求随着涂料用量的 扩大而不断增加， 例如要求低气味低迁移的涂料在纸张、 地板等民用领域使用 非常广泛， 尤其是对于食品药品包装材料有更加严格的检测标准限定了物质迁 移量， 将许多小分子量物质排除在允许的清单之外， 如二苯曱酮， 2 -羟基 -2 曱 基-苯基- 1-丙酮， 苯曱酰基甲酸曱酯、 乙酯等化合物的分子量小， 在组合物施 工中和聚合后， 它们都有可能向接触物迁移或向空气中挥发而造成污染。 所以， 专利 US4507187披露了带有硅氧烷的苯曱酰基甲酸酯， US 3930868和 US4308394 披露了带有丙烯酸酯基团的取代苯曱酰基甲酸酯通过双键聚合连接到树脂上， 从而减低了挥发性。 这样的制备过程显然比较复杂， 增加了材料的成本， 并降 低了材料的通用性。 W09833761披露了乙二醇、 二乙二醇的二苯曱酰甲酸酯作为 非挥发性光引发剂， 实际上， 乙二醇二苯甲酰甲酸酯的分子量只有 326 , 二乙二 醇二苯甲酰曱酸酯的分子量是 370, 在受热挥发性上并不很理想， 仍然能感知到 较明显的气味， 实测热失重分析表明， 200 °C损失 10%， 250 °C已有 20%重量损 失， 300 "C时损失 50%。 而多聚乙二醇醚二苯曱酰曱酸酯由于醚链水溶性较大， 在制造过程中容易乳化和水溶损失； 作为光引发剂使用中， 也是容易被水所浸 溶迁移， 所以并不是一个具有优良实用性的化合物。 发明内容
本申请的目的是提供一类低挥发性的化合物如结构式 I所示
Figure imgf000003_0001
其中 π=2- 10;
Ri为氢原子、 C「C„烷基、 苯基或 0R2; ^为 - C4烷基、 羟基乙基；
-^烷基为直链或支链的， 例如曱基、 乙基、 正丙基、 正丁基、 异丙基、 异丁 基、 叔丁基。 优选的结构式 I化合物， 其中 n=2-6 , ^为氢原子， 与苯曱酰基甲 酸甲酯比较， 它们已经具有非常低的挥发性， 这类化合物可以单独作为光引发 剂或与其它光引发剂混合用于不饱和碳碳双键类化合物的光致聚合过程。
本申请式 I化合物的制备是首先合成笨曱酰基曱酸曱酯或取代苯曱酰基曱 酸曱酯， 然后与二聚或多聚 1， 4 -丁二醇或它们的混合物在催化剂作用下发生酯 交换反应， 催化剂是酯交换反应常用的例如曱醇钠、 乙醇钠、 二丁基氧化锡或 对曱苯磺酸。 反应液的处理过程通常是本领域技术人员熟知的洗涤、 蒸馏等。 式 I化合物之一或几种混合作为光引发剂与至少一种可以进行自由基聚合的、 含 有不饱和碳碳双键的化合物构成组合物， 可以发生光致聚合作用。 含有不饱和 碳碳双键的化合物之一是指一元醇或多元醇及其他结构多元醇的丙烯酸酯， 例 如己二醇二丙烯酸酯、 聚酯多元醇丙烯酸酯； 其次包括乙烯基醚、 乙烯基苯等； 另外还有不饱和二元羧酸的酯、 酰胺等。
除式 I化合物之外， 在组合物中还可以含有其他类型的已知光引发剂的一种 或两种以上混合物以及改善组合物性能的添加剂； 已知的光引发剂有二苯甲酮、 2-异丙基硫杂蒽酮、 2 -羟基 -2-曱基-苯基 -1-丙酮、 1-羟基环己基苯基甲酮、 1 - 曱基- 2- ( 4-吗啉基）一 ( 4-曱硫基）苯基 -1-丙酮 2, 4 , 6-三曱基苯甲酰基二苯基 氧化膦等； 添加剂包含作为稳定剂的物质例如对甲氧基酚、 2- ( 2， -羟基 -5' - 叔丁基苯基） 苯并三唑； 作为聚合促进剂的物质例如三乙醇胺、 对二曱氨基苯 曱酸酯。 在组合物中加入颜料， 可以制备出相应颜色的油墨。
式]化合物的用量占组合物重量的 0. 1-10% ,通常情况下的用量是 1-6%即可 发挥很好的光致聚合作用。
所制备的组合物可以设计成适于使用在各种基材表面上， 例如纸张、 木材、 塑料、 金属， 并以本领域技术人员通常使用的方法涂布和照射光线， 完成固化 过程， 效果是固化前的组合物和固化后的漆膜都只有非常低的气味。 具体实施方式
以下的非限定性例子将进一步说明本申请内容， 但本申请权利要求的内容 并不限于所列举的实施例。
对照卖施例 1
按照专利文献 W09833761的方法，制备二乙二醇二苯甲酰曱酸酯，即将 164g 苯甲酰基甲酸甲酯、 1 06g二乙二醇和 10g二丁基氧化锡混合搅拌加热到 120 "C , 并蒸馏出甲醇， 最后减压蒸馏除去多余苯甲酰基曱酸曱酯， 得到黄绿色液体， 高压液相色谱分析其中含苯曱酰基曱酸甲酯 2% , 含二乙二醇单苯曱酰基甲酸酯 20% , 含二乙二醇双苯曱酰基甲酸酯 78%。 实施例 1
一缩二丁二醇双苯曱酰曱酸酯
在 500毫升四口瓶中， 加入 40.6克（ 0.25摩尔）一缩二丁二醇、 82.5克 （ 0.5 摩尔） 苯曱酰基曱酸曱酯和曱醇钠 4g， 升温到 130Ό搅拌反应 5小时， 同时回 收曱醇。 降温后用水洗涤， 减压蒸除水分， 得 104.5 克浅黄色液体产物。 高压 液相色谱分析剩余苯曱酰基甲酸曱酯含量 0.50%,一缩二丁二醇双苯曱酰甲酸酯 含量为 98.5%, 收率为 98%。 元素分析实测值 (理论值）， C: 67.28% ( 67.59% )、 II： 6.11% ( 6.14% )0 核磁共振氢谱数据见表 1; 结构指认见图 1
表 1 一缩二丁二醇双苯曱酰曱酸酯核磁共振氢谱数据
Figure imgf000005_0001
图 1_ 核磁共振氢谱数据与结构指认
Figure imgf000005_0002
实施例 1
在 500毫升四口瓶中， 加入 125.0克（0.5摩尔） 聚丁二醇 250 (含有一缩 二丁二醇 33%, 二缩三丁二醇 38%， 三缩四丁二醇 22%， 四缩五丁二醇 6%， 五 缩六丁二醇 1%)、 165.0克 （1.0摩尔）苯曱酰基曱酸曱酯和曱醇钠 8g， 升温到 130序号"C 8 251. 3 1 搅拌反应 小时，同时回收曱醇。降温后用水洗涤，减压蒸除水分，得 克浅黄色产物。 高压液相色谱分析剩余苯甲酰基甲酸甲酯含量 1.10%, 所有双酯 含量合计为 98.15%, 收率为 97.4%。
表 2 液相色谱-质 联用分析结果
Figure imgf000006_0001
实施例 3
热失重分析
用美国 ΛΤ仪器公司 Q5000热失重仪实测分析数据表明， 苯曱酰基甲酸甲酯 (MBF )在 120。C损失 50%, 140°C即完全挥发；对照实施例 1的样品 200°C损失 1.0%, 25(TC已有 22%重量损失， 300°C时损失 50°/。； 而实施例 1的样品 200°C只损失 2%， 25(TC只损失 5%重量， 30(TC时损失 20%, 说明实施例 1的样品具有显著耐热性改 善， 挥发性极低。 数据图见图 2。
Figure imgf000007_0001
实施例 4
固化性能比较
将按上述实施例 1和对照实施例 1.所制得的产物及苯曱酰基曱酸甲酯作为光引 发剂制成相应的紫外线固化清漆组合物。 所述组合物的配方见表 3。
Figure imgf000007_0002
将配制所得的清漆组合物用 10微米线棒涂布器施印到马口铁板上， 用一台 功率为 6 ϋ瓦 /厘米中压水银弧光灯以 100米 /分速度进行固化。 纪录获得良好的 表面及彻底固化所需要的灯下通过次数。 其结果如表 4所示。 将配制的清漆用 ΐ ϋ微米线棒涂布器施印到马口铁板上， 用一台功率为 ]. () 0 瓦 /厘米中压水银弧光灯以 100 米 /分速度进行固化。 记录获得良好的表面及彻 底固化所需要的灯下通过次数。 气味最大为 5级， 最小为 1级。 结果如表 4所 示。
表 4 不同光引发剂的评价结果
Figure imgf000008_0001
结果表明本申请的化合物固化后的膜臭味显著低于苯曱酰基曱酸曱酯， 也低于 对照实施例 1的化合物。

Claims

1. 一类结构式 I的化合物，
Figure imgf000009_0001
其中 n=2 ~ 10;
^为氢原子、 - 烷基、 苯基或 0R2; ！^为 - C4烷基、 羟基乙基。
2. 权利要求 1的化合物，
其中 n=2 ~ 6;
^为氢原子。
3. 一种光致聚合组合物， 组成有：
(a) 至少一种可以进行自由基聚合的、 含有不饱和碳碳双键的化合物和
(b) 至少一种作为光引发剂的根据权利要求 1的结构式 I的化合物。
4. 根据权利要求 3的组合物，在此基础上还含有其它已知光引发剂作为组分（ c ) 和其他添加剂作为组分（d)，
其中组分（c)是二苯甲酮类、 ex-羟基酮类、 α-氨基酮类或酰基氧化膦类之一 或其混和物。
5. 根据权利要求 3或 4的一种组合物， 其中组分（ b ) 的重量含量 0.1-10%.,
PCT/CN2010/000949 2010-06-25 2010-06-25 低挥发性苯甲酰基甲酸酯 WO2011160262A1 (zh)

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CN101523289A (zh) * 2006-10-03 2009-09-02 西巴控股有限公司 包含苯甲酰甲酸酯型光引发剂的可光固化组合物

Cited By (2)

* Cited by examiner, † Cited by third party
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EP3392709A1 (en) * 2017-04-21 2018-10-24 Agfa Nv A lithographic printing plate precursor
WO2018192932A1 (en) * 2017-04-21 2018-10-25 Agfa Nv A lithographic printing plate precursor

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