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WO2019101142A1 - 二丁基芴基衍生物与其作为光引发剂的应用 - Google Patents

二丁基芴基衍生物与其作为光引发剂的应用 Download PDF

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Publication number
WO2019101142A1
WO2019101142A1 PCT/CN2018/116999 CN2018116999W WO2019101142A1 WO 2019101142 A1 WO2019101142 A1 WO 2019101142A1 CN 2018116999 W CN2018116999 W CN 2018116999W WO 2019101142 A1 WO2019101142 A1 WO 2019101142A1
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Prior art keywords
photocurable composition
compound
photoinitiator
methyl
composition according
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PCT/CN2018/116999
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English (en)
French (fr)
Inventor
林剑雄
陈传文
Original Assignee
惠州市华泓新材料股份有限公司
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Priority to US16/765,826 priority Critical patent/US11560362B2/en
Application filed by 惠州市华泓新材料股份有限公司 filed Critical 惠州市华泓新材料股份有限公司
Priority to JP2020545844A priority patent/JP7059384B2/ja
Priority to EP18881958.5A priority patent/EP3715381B1/en
Publication of WO2019101142A1 publication Critical patent/WO2019101142A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/108—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
    • C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate

Definitions

  • This invention relates to the field of radiation light irradiation curing.
  • the present invention provides a novel dibutyl decyl derivative: 2-methyl-1-(2-(9,9-dibutylfluorenyl))-2-(N-morpholinyl)- 1-Acetone and its preparation method, and 2-methyl-1-(2-(9,9-dibutyldecyl))-2-(N-morpholinyl)-1-propanone as photoinitiator application.
  • UV curing technology refers to a new technology that uses ultraviolet light (UV) and electron beam (EB), infrared light, visible light, laser, chemical fluorescence and other radiation to illuminate the polymer. It is highly efficient, economical, energy-saving and environmentally friendly. It belongs to new energy saving and environmental protection technology.
  • UV ultraviolet light
  • EB electron beam
  • Photoinitiators are widely used in the domestic coatings and ink industries. As people's living standards improve, more and more attention is paid to environmental and food safety issues. Color printing in the packaging industry, especially in the food and cosmetic packaging industry, is becoming more and more restrictive for harmful volatile organic compounds (VOC) such as benzene, carbon tetrachloride and chloroform. For example, the printing of food packaging strictly stipulates that the maximum amount of benzene released is limited to 3 mg/m 2 and the package of tobacco packaging is 0.01 mg/m 2 . The relevant standards of the United States and Europe are more stringent. China is a large industrial manufacturing country. The export volume of packaging products to the US and European countries is increasing. The detection limit of harmful volatile organic compounds in packaging products must meet the standards of the US and European countries.
  • VOC volatile organic compounds
  • the commonly used photoinitiators such as benzophenone and diphenylethylenedione, can produce volatile organic compounds due to light-induced effects during use, and currently fail to meet the testing standards in the field of food and cosmetic packaging.
  • Some photoinitiators of some carbazole and dibenzofuran compounds have poor stability during storage and use, and because of the high cost of raw materials used such as carbazole and dibenzofuran. Therefore, the photoinitiator is costly and has no special advantage in performance.
  • the photoinitiators of the prior art also have low photoinitiation inefficiencies, particularly those which have a certain limitation on the wavelength requirements of the initiating light source and low light inducing efficiency in some wavelength ranges.
  • the present invention provides a novel compound as a photoinitiator.
  • the present invention also provides a photocurable composition containing the novel compound, and a curing method using the novel compound and the photocurable composition.
  • the compound, the curing composition and the photocuring method provided by the invention can more effectively initiate photopolymerization in the wavelength range, and the compound provided by the invention has higher stability, is easy to prepare and process, and is more environmentally friendly. .
  • the present invention provides a photocurable composition
  • a photocurable composition comprising:
  • the photoinitiator compound of the photocurable composition of the invention comprises from 0.5% to 10%, preferably about 3% by weight of the composition.
  • the photopolymerizable carbon-carbon double-bonded unsaturated compound of the component (b) in the photocurable composition of the present invention includes a compound having one or more olefinic double bonds.
  • the photopolymerizable compound monomer include: alkyl acrylate, alkyl methacrylate, hydroxyalkyl ester, alkylene oxide, (meth)acrylamide, N-substituted (meth) propylene An amide, an unsaturated carboxylic acid anhydride, an unsaturated ester, a vinyl ether, an isocyanurate, an N-vinyl heterocyclic compound, or the like.
  • the ethylenically unsaturated photopolymerizable compound is an ester of an ethylenically unsaturated carboxylic acid with a polyol or polyepoxide.
  • the unsaturated carboxylic acid are acrylic acid, methacrylic acid, unsaturated fatty acids such as linolenic acid or oleic acid.
  • the unsaturated carboxylic acid is acrylic acid and methacrylic acid.
  • the polyol can be an aromatic, aliphatic or cycloaliphatic polyol.
  • the aromatic polyol examples include hydroquinone, 4,4-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, and novolac resin and phenol resin A.
  • the ethylenically unsaturated photopolymerizable compound is an acrylated epoxy resin, an alkyl acrylate, an alkoxy acrylate or a mixture thereof, most preferably an epoxy acrylate, Trimethylolpropane triacrylate or a mixture thereof.
  • the ethylenically unsaturated photopolymerizable compound in the component (b) may be one of them, a mixture of two or a mixture of two or more thereof.
  • the component (b) ethylenically unsaturated photopolymerizable compound is generally used in an amount of from about 10% to about 70%, preferably from about 25% to about 60%.
  • additives may also be included in the photopolymerizable composition provided by the present invention.
  • a thermal inhibitor that prevents premature polymerization e.g., a UV absorber
  • Light stabilizers such as hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone and the like can be used.
  • the photocurable composition of the present invention further comprises a reactive amine co-initiator, such as a water soluble tertiary amine.
  • a reactive amine co-initiator such as a water soluble tertiary amine.
  • the amine co-initiator comprises from 0.5 to 10%, preferably about 7% by weight of the composition.
  • the photocurable composition of the invention comprises:
  • the percentage is the weight ratio of the composition.
  • the present invention provides a method for curing a photocurable composition of the present invention, which comprises applying the photocurable composition onto a substrate and irradiating with light having a wavelength of from 150 to 600 nm.
  • the photocurable composition of the invention is particularly suitable for curing at light irradiation radiation having a wavelength of from 320 to 420 nm.
  • Examples of light sources or radiation that can be used in the curing method of the aspects of the present invention include a mercury vapor lamp or a laser lamp that emits a band between the UV-visible regions.
  • the present invention provides the use of the above-described photocurable compositions of the present invention for the manufacture of pigmented and non-pigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, electronics Photoresist, electroplated resist, liquid film and dry film, solder resist, resist for color filter for display applications, production in plasma display panels, electroluminescent displays, and LCD manufacturing processes Structural resists, LCD spacers, holographic data storage, compositions for encapsulating electrical and electronic components, for the manufacture of magnetic recording materials, micromechanical components, optical switches, electroplating masks, etch masks, Color proofing system, fiberglass cable coating, screen printing stencil, for producing three-dimensional objects by stereolithography, for image recording materials, for holographic recording, microelectronic circuits, decolorizing materials, images for using microcapsules Record material.
  • the present invention also provides at least one coated substrate having a surface coated with the above-described photocurable composition of the present invention.
  • the method includes the following steps:
  • step (5) comprises: mixing 2-methyl-1-methoxy[2-(9,9-dibutyldecyl)propene oxide with morpholine, stirring After refluxing for about 20 hours, excess morpholine was distilled off under reduced pressure, and the residue was dissolved in methanol, dissolved by heating, and allowed to stand and cool.
  • the method of the present invention for preparing the compound has the characteristics of high yield, material saving, and cost reduction.
  • the photoinitiator compound molecule has a longer light absorption wavelength, and the wavelength of the light used for the use is longer. Compared with the requirements of other photoinitiators requiring shorter wavelengths and higher energy, the requirement for light energy is reduced. The light source range is wider, the light utilization efficiency is higher, and the use is more convenient.
  • the molecular structure of the photoinitiator compound molecule makes it more soluble in an organic solvent, which is convenient for practical use.
  • the photoinitiator compound molecule has higher stability relative to a photoinitiator having other heteroatoms, and since the method of preparing the compound of the present invention uses a lower raw material cost than a photoinitiator having other heteroatoms, Has a comparative advantage in cost price and performance.
  • a methanol solution of sodium methoxide was prepared by adding 50 mL of anhydrous methanol and 0.12 mol (2.76 g) of sodium metal in a 250 mL three-necked flask. The temperature was controlled to add 0.10 mol (4.27 g) of 2-(2-bromo-2-methylpropionyl)-9,9-dibutylfluorene in three portions over 1.5 to 2.0 hours at 25-30 °C. After the addition was completed, the reaction was continued for 1 hour. After the reaction of 2-(2-bromo-2-methylpropanoyl)-9,9-dibutylfluorene was completely determined by HPLC, the solvent methanol was removed by rotary distillation at 60 ° C to afford a white solid. The product was directly subjected to the next step without purification.
  • Method 1 The product of the reaction of the step (4) was obtained by adding 3.87 g (10.0 mmol) of 2-methyl-1-methoxy[2-(9,9-dibutyldecyl)propene oxide to a 100 mL reaction flask. To the morpholine 2.61 g (30.0 mmol), the reaction was stirred at 120-130 ° C for 20 hours.
  • the target product was determined to be 2-methyl-1-(2-(9,9-dibutylfluorenyl))-2-(N-morpholinyl). 1-acetone.
  • Method 2 does not require column chromatography to separate and purify the product, and is more suitable for industrial production.
  • the photocurable varnish formulation was formulated according to the following formulation.
  • the inventive preparation was prepared by using 2-methyl-1-(2-(9,9-dibutyldecyl))-2-(N-morpholinyl)-1-propanone as a photoinitiator.
  • Comparative preparations prepared by other photoinitiators were prepared and tested by preparing a photocurable varnish formulation having only the same photoinitiator content and the same formulation.
  • Comparative preparation 1 was prepared by using 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone as a photoinitiator;
  • Comparative Formulation 2 was prepared using 2-methyl-1-(4-biphenyl)-2-morpholinyl-1-propanone as a photoinitiator.
  • the varnish preparation prepared in Example 2 was coated with a printing applicator by a thickness of about 15 ⁇ m on a blank paper, and an ultraviolet lamp with a tunable filter with a power of 50 W/CM was used in the wavelength range of 320-420.
  • the curing was carried out at a speed of 100 m/min, and the number of passes under the lamp required to obtain a good surface and complete curing was recorded. The results are shown in Table 1 below.
  • the amount of VOC released in the cured film prepared by the photoinitiator of the present invention in Example 3 was measured by headspace-gas chromatography.
  • Solid photoinitiator compound of the invention 2-methyl-1-(2-(9,9-dibutyldecyl))-2-(N-morpholinyl)-1-propanone; comparative photoinitiator 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone and 2-methyl-1-(4-biphenyl)-2-morpholinyl-1- acetone
  • a liquid polymerizable monomer (1,6-hexanediol diacrylate (HDDA) or tripropylene glycol diacrylate (TPGDA)
  • HDDA 1,6-hexanediol diacrylate
  • TPGDA tripropylene glycol diacrylate
  • the varnish formulation prepared in Example 2 was applied to a 12 ⁇ 12 cm paperboard using a 15 micron wire bar coater and cured at a speed of 20 m/min with a medium pressure mercury arc lamp at a power of 80 watts/cm.
  • the cardboard was cut into a size of 10 ⁇ 10 cm, completely immersed in two simulated liquids of 100 ml of distilled water and 3% acetic acid aqueous solution, and sealed and placed at 40 ° C for 10 days.
  • the printed matter was taken out, and after standing, the content of the initiator compound in the simulated liquid was directly analyzed by HPLC.
  • the calculation of the mobility measurement results in g/Kg of food was carried out by packaging 1 kg of food in a printing area of 600 cm 2 , and the results are shown in Table 4.
  • the present inventors have surprisingly found that the innovative compound 2-methyl-1-(2-(9,9-dibutyldecyl))-2-(N-morpholinyl)-1-propanone is photopolymerized. It has good properties and is capable of efficiently generating a polymerization initiating group upon irradiation with, for example, ultraviolet (UV) light. Moreover, the photoinitiator compound and the cured composition provided by the invention have low production cost, simple production process, simple post-treatment, and meet environmental protection requirements. The photoinitiator provided by the invention can effectively reduce the release amount of various VOCs in the product, including benzene or toluene, and is suitable for the packaging and printing industries such as food, tobacco and cosmetics.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymerisation Methods In General (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明提供了一种二丁基芴基衍生物和其作为光引发剂的应用以及其制备方法。本发明提供了含有所述化合物的光固化组合物和使用该组合物的光固化方法。

Description

二丁基芴基衍生物与其作为光引发剂的应用 技术领域
本发明涉及辐射光照射固化领域。具体的，本发明提供了新的二丁基芴基衍生物：2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮和其制备方法，以及2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮作为光引发剂的应用。
背景技术
辐射固化技术是指利用紫外光(UV)和电子束(EB)、红外光、可见光、激光、化学荧光等辐射光照射固化聚合物的新型技术，具有高效、经济、节能、环境友好的特点，属于新型节能环保技术。
光引发剂在国内涂料、油墨行业被广泛应用。随着人们生活水平的提高，对环境和食品安全问题越来越重视。包装业，尤其是食品和化妆品包装行业的彩色印刷，对有害挥发性有机物(VOC)，如苯、四氯化碳、氯仿等的限量越来越严格。例如食品包装的印刷就严格规定了苯释放量最高限制为3mg/m 2，烟草包装用品为0.01mg/m 2。美欧国家的相关标准更加严格。我国是工业制造大国，包装行业产品对美欧国家的出口量越来越多，包装产物有害挥发性有机物的检出限量必须满足美欧国家的标准。
现在常用的光引发剂，如二苯甲酮、二苯乙二酮等，由于在使用过程中受光引发作用，会产生挥发性有机物，目前已经不能满足在食品和化妆品包装领域的检测标准要求。现有的某些咔唑和二苯并呋喃类化合物类的光引发剂，在储存、使用时，稳定性较差，同时由于所使用的原材料例如咔唑和二苯并呋喃的成本较高，所以导致光引发剂成本价高，而性能上没有特别优势。
现有技术中的光引发剂还存在光引发效率低，特别是对引发光源的波长要 求具有一定限制，在某些波长范围内光引发效率低的缺陷。
因此，在光聚合技术领域中，还需要对环境更为友好，具有更高活性、容易制备且容易处理等优点的光引发剂和光固化方法。
发明内容
本发明提供了一种作为光引发剂的新的化合物。本发明还提供了一种含有所述新的化合物的光固化组合物，并提供了采用所述新化合物和光固化组合物的固化方法。本发明提供的化合物、固化组合物和光固化方法能够更有效地在波长范围内引发光聚合反应，而且本发明提供的化合物具有更高稳定性，以及易于制备和处理，对环境更为友好的特点。
具体的，本发明提供了一种光固化组合物，其包含：
(a)具有下式的光引发剂化合物
Figure PCTCN2018116999-appb-000001
(b)可光聚合的碳碳双键式不饱和化合物。
在本发明的其中一个方面，本发明的光固化组合物中所述光引发剂化合物占该组合物重量的0.5-10％，优选为约3％。
本发明的光固化组合物中组分(b)的所述可光聚合的碳碳双键式不饱和化合物包括具有一个或多个烯双键的化合物。可光聚合的化合物单体的例子包括：丙烯酸烷基酯、甲基丙烯酸烷基酯、羟烷基酯、环氧烷基酯、(甲基)丙烯酰胺、N-取代的(甲基)丙烯酰胺、不饱和羧酸酐、不饱和酯、乙烯基醚、异氰脲酸酯、N-乙烯基杂环化合物等。
在本发明的一个方面，所述烯属不饱和可光聚合的化合物为烯属不饱和羧酸与多元醇或聚环氧化物的酯。所述不饱和羧酸的例子为丙烯酸、甲基丙烯酸、不饱和脂肪酸如亚麻酸或油酸。优选的，所述不饱和羧酸为丙烯酸和甲基丙烯 酸。所述多元醇可为芳族，脂族或环脂族多元醇。芳族多元醇的例子为对苯二酚、4,4-二羟基联苯、2,2-二(4-羟基苯基)丙烷、以及线型酚醛树脂和酚醛树脂A。在本发明的另一个方面，所述烯属不饱和可光聚合的化合物为丙烯酸酯化的环氧树脂、丙烯酸烷基酯、丙烯酸烷氧基酯或其混合物，最优选为环氧丙烯酸酯、三羟甲基丙烷三丙烯酸酯或其混合物。
组分(b)中所述烯属不饱和可光聚合的化合物可以是其中的一种，也可以是其中的两种的混合物或是两种以上的混合物。
在本发明的可光聚合的组合物中，组分(b)烯属不饱和可光聚合的化合物一般用量为约10％至约70％，优选为约25％至约60％。
本发明提供的可光聚合的组合物中还可含有其它添加剂。例如防止过早聚合的热抑制剂、光稳定剂(如紫外线吸收剂)等。可使用的光稳定剂例如羟基苯基苯并三唑、羟基苯基-二苯甲酮等。
在本发明的其中又一个方面，本发明的光固化组合物中还含有反应性胺助引发剂，例如为水溶性叔胺类。所述胺助引发剂占该组合物重量的0.5-10％，优选为约7％。
在本发明的其中又一个方面，本发明的光固化组合物包含：
Figure PCTCN2018116999-appb-000002
其中所述百分比为其在组合物中所占重量比。
本发明提供了上述本发明的光固化组合物的固化方法，包括将所述光固化组合物涂布在基材上，用波长在150-600nm的光进行照射。在本发明的其中一个方面，本发明的光固化组合物的特别适合在波长在320-420nm的光照射辐射进行固化。可用于本发明方面的固化方法的光源或辐射的例子包括发射波段在UV-可见光区之间的汞蒸气灯或者激光灯。
本发明提供了上述本发明的光固化组合物的应用，用于制造着色和非着色的油漆和清漆、粉末涂料、印刷油墨、印刷板、粘合剂、牙科组合物、凝胶涂料、电子学用光致抗蚀剂、电镀抗蚀剂、液体膜和干膜、阻焊剂、显示应用的滤色片用的抗蚀剂、在等离子体显示板、电致发光显示器和LCD的制造过程中产生结构用的抗蚀剂、LCD间隔物、用于全息数据存储、作为包封电气和电子元件的组合物、用于制造磁记录材料、微机械部件、光学开关、电镀掩模、蚀刻掩模、色彩打样体系、玻璃纤维电缆涂料、丝网印刷模版、用于通过立体平版印刷技术产生三维物体、用作图像记录材料、用于全息记录、微电子电路、脱色材料、用于使用微胶囊的图像记录材料。
本发明还提供了至少一个表面上涂有上述本发明的光固化组合物的涂布基材。
在本发明的其中一个方面，提供了具有下式的光引发剂化合物
Figure PCTCN2018116999-appb-000003
在本发明的其中一个方面，提供了制备下式化合物的方法，
Figure PCTCN2018116999-appb-000004
所述方法包括以下步骤：
Figure PCTCN2018116999-appb-000005
Figure PCTCN2018116999-appb-000006
在本发明的其中一个方面，其中步骤(5)包括：将2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉混合，搅拌回流反应约20小时，减压蒸馏出多余的吗啉，加入甲醇溶解剩余物，加热溶解后，静置、冷却。本发明的制备所述化合物的方法具有产率高、节省原料和降低成本的特点。
本发明的光引发剂化合物和包含所述光引发剂化合物的光固化组合的优点包括：
1.所述光引发剂化合物分子的光吸收波长较长，引发使用的灯光波长也较长，与其它光引发剂需要的波长短、能量高的要求比较，降低了对光能量的要求，可用光源范围更广，光利用效率更高，使用更方便。
2.所述光引发剂化合物分子的分子结构使其在有机溶剂的溶解度更高，方便实际应用。
3.所述光引发剂化合物分子相对具有其它杂原子的光引发剂的稳定性较高，同时由于本发明的化合物的制备方法使用的原材料成本较具有其它杂原子的光引发剂的低，因此具有成本价格和性能上的比较优势。
具体实施方式
通过下述实施例有助于进一步理解本发明，但不用于限制本发明的内容。
实施例1 2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮的合成
2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮的合成路径如下所示：
Figure PCTCN2018116999-appb-000007
步骤(1)9,9-二丁基芴的合成：
于100mL三颈烧瓶中分别加入12mmol(1.99克)芴、0.5mmol(0.16克)相转移催化剂四正丁基溴化铵、4.5mL 50％的氢氧化钠水溶液，29mmol(3.1mL)正溴丁烷和50mL丁酮。加热回流3-4小时，并以薄层层析跟踪反应，直至反应结束。蒸馏除去溶剂丁酮后，用二氯甲烷萃取(10mL x 3次)。合并有机层，用无水硫酸钠干燥，旋转蒸发除去溶剂后得到目标产物。
步骤(2)2-(2-甲基丙酰基)-9,9-二丁基芴的合成：
于250mL三颈烧瓶中分别加入0.01mol(1.0mL)异丁酰氯、0.01mol(2.78克)9,9-二丁基芴和40mL二氯甲烷。磁力搅拌混合均匀，并以冰浴冷却。磁力搅拌下，于10℃以下分二次加入总计为0.012mol(1.58克)的三氯 化铝，后升温至室温搅拌3小时，再升温至40℃继续搅拌1小时。搅拌下把反应混合物慢慢倒入100克冰水中。静置分层后，分离除去水层，有机层用冰水洗涤(30mL x 3次)，基本呈中性。干燥后除去二氯甲烷得到目标产物。
步骤(3)2-(2-溴-2-甲基丙酰基)-9,9-二丁基芴的合成：
往250mL的三口烧瓶中加入二氯甲烷50mL，15mL 80％的硫酸，0.20mol的双氧水和0.10mol(34.85克)的2-(2-甲基丙酰基)-9,9-二丁基芴。温度控制在25-30℃，1.0-1.5小时内滴加0.07mol(3.6mL)溴素。滴加完毕溴素20分钟后HPLC检测2-(2-甲基丙酰基)-9,9-二丁基芴反应完全。冷却下，搅拌滴加30％的氢氧化钠溶液，中和上述反应混合物值pH为中性。静置、分层。水层用二氯甲烷萃取(20mL x 2次)。合并有机层，干燥、旋转蒸馏除去溶剂二氯甲烷，得到目标产物。
步骤(4)2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷的合成：
在250mL的三口烧瓶中加入50mL无水甲醇和0.12mol(2.76克)金属钠，制备出甲醇钠的甲醇溶液。温度控制在25-30℃，1.5-2.0小时内分三批加入0.10mol(4.27克)2-(2-溴-2-甲基丙酰基)-9,9-二丁基芴。加入完毕后，继续反应1小时。HPLC检测2-(2-溴-2-甲基丙酰基)-9,9-二丁基芴反应完全后，60℃旋转蒸馏除去溶剂甲醇，冷却得到白色固体。产物不经纯化，直接进行下步反应。
步骤(5)2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮的合成：
方法1：取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷3.67g(10.0mmol)加入100mL反应瓶中，加入吗啉2.61g(30.0mmol)，于120-130℃搅拌反应20小时。点板跟踪反应结束后减压蒸馏出多余的吗啉等溶剂后，以石油醚-乙酸乙酯为流动相柱层析分离纯化得到目标化合物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮3.63g，产率83.7％。1H NMR(400MHz,CDCl3)δ:8.74(d,J＝0.8Hz,1H),8.48(dd,J1＝8.0Hz,J2＝0.8Hz,1H), 7.78-7.73(m,2H),7.39-7.37(m,3H),3.74(t,J＝4.8Hz,4H),2.66-2.64(m,4H),2.05-2.00(m,4H),1.59(s,6H),1.13-1.06(m,4H),0.69-0.60(m,10H)；13C NMR(100MHz,CDCl3)δ:202.9,151.9,149.8,145.2,140.0,129.6,128.1,127.0,125.0,123.0,120.6,119.0,76.9,67.4,55.0,47.1,40.1,26.0,23.0,20.4,13.8.ESRMs m/z＝434.3[M+H]+。
根据核磁共振谱(氢谱、碳谱)和质谱结果确定为目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮。
方法2.取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷7.33g(20.0mmol)加入100mL反应瓶中，加入吗啉4.35g(50.0mmol)，搅拌回流反应20小时。点板跟踪反应结束后减压蒸馏出多余的吗啉后，加入甲醇溶解剩余物，加热使其完全溶解后，静置、冷却，得到目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮7.14g，产率82.3％。
根据核磁共振谱(氢谱、碳谱)和质谱结果与合成方法1相同，即为目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮。
方法3.取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷7.33g(20.0mmol)加入100mL反应瓶中，加入吗啉1.74g(20.0mmol)，N,N-二甲基甲酰胺10mL，搅拌回流反应20小时。后处理同合成方法2，得到目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮5.04g，产率58.1％。
方法4.取步骤(4)反应的产物2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷7.33g(20.0mmol)加入100mL反应瓶中，加入吗啉1.74g(100.0mmol)，搅拌回流反应20小时。后处理同合成方法2，得到目标产物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮7.32g，产率84.4％。
其中，方法1的产物收率(83.7％)稍高于方法2的产物收率(82.3％)。方法2不需要柱层析分离纯化产物，更适宜工业化生产。
方法3中，反应原料2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉的摩尔比为1:1时，产率低，只有58.1％；同时也由于2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷常温下为固体，二个反应原料相互溶解充分性稍差。
方法4中，反应原料2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉的摩尔比为1:5时，产物收率(84.4％)与合成方法2的收率(82.3％)没有明显提升，但是吗啉的摩尔比用量由2.5提升到5.0，吗啉的用量明显增加。
实施例2光固化清漆制剂的制备
根据以下配方配置光固化清漆制剂。
具体配方如下：
Figure PCTCN2018116999-appb-000008
根据上述配方，以2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮作为光引发剂制备得到发明制剂。
通过制备只有光引发剂含量不同，其它配方组成都一样的光固化清漆制剂来制备和测试其它光引发剂制备得到的对比制剂。
包括：
以2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮作为光引发剂制备得到对比制剂1；
以2-甲基-1-(4-联苯基)-2-吗啉基-1-丙酮作为光引发剂制备得到对比制剂2。
实施例3固化效果测试
将实施例2中配制所得的清漆制剂用印刷适性仪涂布约15微米厚度于空白纸张上，用功率为50W/CM线功率的带可调过滤器的紫外灯，在320-420波长范围下，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。结果如下表1所示。
表1紫外线照射固化效果测定结果
Figure PCTCN2018116999-appb-000009
实施例4VOC释放分析
采用顶空-气相色谱法测定实施例3中用本发明的光引发剂制备的固化膜中的VOC释放量。
结果如下表2所示。
表2顶空-气相色谱法测定涂层固化层有害VOC的释放量测定结果
Figure PCTCN2018116999-appb-000010
Figure PCTCN2018116999-appb-000011
实施例5溶解度、黄变和气味分析
将固态光引发剂(本发明化合物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮；对比光引发剂2-甲基-1-[4-甲硫基苯基]-2-吗啉基-1-丙酮和2-甲基-1-(4-联苯基)-2-吗啉基-1-丙酮
Figure PCTCN2018116999-appb-000012
)溶入液体聚合单体(1,6-己二醇二丙烯酸酯(HDDA)或二缩三丙二醇二丙烯酸酯(TPGDA))中，加热至50～60℃并混合均匀。溶解后的液体应在室温下贮存。测量其溶解度。观察黄变程度和人工评估气味。结果如下表3。
表3溶解度黄变和气味分析测定结果
Figure PCTCN2018116999-appb-000013
实施例6稳定性分析
将实施例2配制所得的清漆制剂用15微米线棒涂布器施印到12╳12cm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。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分析模拟液中引发剂化合物含量。按600cm 2印刷面积包装1kg食品计算，迁移率测量结果以g/Kg食品表示，其结果如表4所示。
表4稳定性分析结果
Figure PCTCN2018116999-appb-000014
本发明出人意料地发现，创新性的化合物2-甲基-1-(2-(9,9-二丁基芴基))-2-(N-吗啉基)-1-丙酮在光聚合反应中具有良好的性能，能够有效地在例如紫外(UV)光的照射时产生聚合引发基。而且本发明提供的光引发剂化合物和固化组合物的生产成本低，同时生产工艺简单，后处理简单，满足环境保护要求。本发明提供的光引发剂可以有效降低产品中各种VOC，包括苯或甲苯的释放量，适合应用于食品、烟草、化妆品等包装印刷行业。

Claims (10)

  1. 一种光固化组合物，其包含：
    (a)具有下式的光引发剂化合物
    Figure PCTCN2018116999-appb-100001
    (b)可光聚合的碳碳双键式不饱和化合物。
  2. 权利要求1的光固化组合物，其中所述光引发剂化合物占该组合物重量的0.5-10％，优选为约3％。
  3. 根据权利要求1的光固化组合物，其中所述碳碳双键式不饱和化合物为烯属不饱和羧酸与多元醇的酯或烯属不饱和羧酸与聚环氧化物的酯。
  4. 根据权利要求1-3中任一项的光固化组合物，其还含有反应性胺助引发剂，例如为水溶性叔胺类，所述胺助引发剂占该组合物重量的0.5-10％，优选为约7％。
  5. 根据权利要求1的光固化组合物，其包含：
    Figure PCTCN2018116999-appb-100002
    其中所述百分比为其在组合物中所占重量比。
  6. 根据权利要求1-5中任何一项的光固化组合物的应用，用于制造着色和非着色的油漆和清漆、粉末涂料、印刷油墨、印刷板、粘合剂、牙科组合物、凝胶涂料、电子学用光致抗蚀剂、电镀抗蚀剂、液体膜和干膜、阻焊剂、显示应用的滤色片用的抗蚀剂、在等离子体显示板、电致发光显示器和LCD的制造过程中产生结构用的抗蚀剂、LCD间隔物、用于全息数据存储、作为包封电 气和电子元件的组合物、用于制造磁记录材料、微机械部件、光学开关、电镀掩模、蚀刻掩模、色彩打样体系、玻璃纤维电缆涂料、丝网印刷模版、用于通过立体平版印刷技术产生三维物体、用作图像记录材料、用于全息记录、微电子电路、脱色材料、用于使用微胶囊的图像记录材料。
  7. 权利要求1-5中任何一项的光固化组合物的固化方法，包括将所述光固化组合物涂布在基材上，用波长在150-600nm范围的光进行照射，优选用波长在320-420nm范围的光进行照射。
  8. 一种具有下式的光引发剂化合物
    Figure PCTCN2018116999-appb-100003
  9. 一种制备下式化合物的方法，
    Figure PCTCN2018116999-appb-100004
    包括以下步骤：
    Figure PCTCN2018116999-appb-100005
    Figure PCTCN2018116999-appb-100006
  10. 根据权利要求9的方法，其中步骤(5)包括：将2-甲基-1-甲氧基[2-(9,9-二丁基芴基)]环氧丙烷和吗啉混合，搅拌回流反应约20小时，减压蒸馏出多余的吗啉，加入甲醇溶解剩余物，加热溶解后，静置、冷却。
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