WO2021121135A1 - Photoinitiator, preparation method therefor and application thereof, and photocurable composition - Google Patents

Photoinitiator, preparation method therefor and application thereof, and photocurable composition Download PDF

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Publication number
WO2021121135A1
WO2021121135A1 PCT/CN2020/135471 CN2020135471W WO2021121135A1 WO 2021121135 A1 WO2021121135 A1 WO 2021121135A1 CN 2020135471 W CN2020135471 W CN 2020135471W WO 2021121135 A1 WO2021121135 A1 WO 2021121135A1
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Prior art keywords
alkyl
substituted
group
photoinitiator
cycloalkyl
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PCT/CN2020/135471
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French (fr)
Chinese (zh)
Inventor
钱晓春
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常州强力电子新材料股份有限公司
常州强力先端电子材料有限公司
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Priority claimed from CN201911319513.8A external-priority patent/CN113004440B/en
Priority claimed from CN201911320729.6A external-priority patent/CN113004738B/en
Application filed by 常州强力电子新材料股份有限公司, 常州强力先端电子材料有限公司 filed Critical 常州强力电子新材料股份有限公司
Publication of WO2021121135A1 publication Critical patent/WO2021121135A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/16—Quinones the quinoid structure being part of a condensed ring system containing three rings
    • C07C50/18—Anthraquinones, i.e. C14H8O2
    • 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
    • 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
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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

Definitions

  • UV curing technology has become the focus of today's society due to its outstanding advantages such as short curing time, fast speed, energy saving, and low pollution.
  • the light source used in traditional UV curing is mainly high-pressure mercury lamp, but it has the defects of low energy efficiency, large heat generation, short service life, ozone pollution, and heavy metal mercury. Therefore, the development and use of new energy-saving and environmentally friendly curing light sources is a general trend.
  • UV-LED light source has the characteristics of high luminous efficiency, long use time, energy saving and environmental protection, and less heat. It overcomes the shortcomings of traditional light sources and is favored by more and more people, making it a new type of UV curing method.
  • the UV-LED curing system consists of oligomers, active monomers, photoinitiators and additives.
  • the photoinitiator is the key component of the curing system, which has a significant impact on the various properties of light curing.
  • the UV-LED curing method has many advantages as above, the UV-LED light source emits more than 365nm wavelength, which brings huge challenges to traditional photoinitiators.
  • the above-mentioned photoinitiators are mainly small-molecule initiators, which have a migration risk, especially in food, medicine and other packaging materials that may have a health risk, so they need to be reduced to a minimum.
  • R 1 and R 2 are each independently selected from C 1 ⁇ C 20 linear alkyl, C 1 ⁇ C 20 branched alkyl, C 3 ⁇ C 20 cycloalkyl, C 3 ⁇ C 8 Cycloalkyl substituted C 1 to C 12 alkyl, C 6 to C 20 aryl substituted C 1 to C 12 alkyl, and C 1 to C 12 alkyl substituted C 3 to C 8 ring Any of the alkyl groups, R 1 and R 2 can be connected to each other to form a ring; R 3 is a photoactive group; each of the two Ar is independently selected from substituted or unsubstituted arylene or substituted or unsubstituted Any one of the heteroarylene groups;
  • R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are each independently selected from hydrogen, C 1 ⁇ C 20 linear alkyl, C 1 ⁇ C 20 Branched chain alkyl group, C 3 ⁇ C 20 cycloalkyl group, C 3 ⁇ C 8 cycloalkyl group substituted C 1 ⁇ C 12 alkyl group, C 1 ⁇ C 12 alkyl group substituted C 3 ⁇ C 8 Cycloalkyl group, C 7 ⁇ C 20 aralkyl group, C 2 ⁇ C 20 heterocyclic group, -OR d1 , -COR d1 , -COOR d1 , -SR d1 , -SO 2 R d1 and -CONR d1 Any one of R d2 , wherein R d1 and R d2 are each independently selected from hydrogen, C 1
  • R e1 and R e2 are each independently selected from hydrogen, C 1 ⁇ C 20 linear alkyl, C 1 to C 20 branched alkyl, C 3 to C 20 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, and -C(R 1 )(R 2 ) Any one of (R 3 ).
  • a photocurable ink including a photocurable composition selected from any one of the above-mentioned photocurable compositions.
  • R 1 and R 2 are each independently selected from C 1 ⁇ C 20 linear alkyl, C 1 ⁇ C 20 branched alkyl, C 3 ⁇ C 20 cycloalkyl, C 3 ⁇ C 8 Cycloalkyl substituted C 1 to C 12 alkyl, C 6 to C 20 aryl substituted C 1 to C 12 alkyl, and C 1 to C 12 alkyl substituted C 3 to C 8 ring Any of the alkyl groups, R 1 and R 2 can be connected to each other to form a ring; R 3 is a photoactive group; each of the two Ar is independently selected from substituted or unsubstituted arylene or substituted or unsubstituted Any one of the heteroarylene groups;
  • R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are each independently selected from hydrogen, C 1 ⁇ C 20 linear alkyl, C 1 ⁇ C 20 Branched chain alkyl group, C 3 ⁇ C 20 cycloalkyl group, C 3 ⁇ C 8 cycloalkyl group substituted C 1 ⁇ C 12 alkyl group, C 1 ⁇ C 12 alkyl group substituted C 3 ⁇ C 8 Cycloalkyl group, C 7 ⁇ C 20 aralkyl group, C 2 ⁇ C 20 heterocyclic group, -OR d1 , -COR d1 , -COOR d1 , -SR d1 , -SO 2 R d1 and -CONR d1 Any one of R d2 , wherein R d1 and R d2 are each independently selected from hydrogen, C 1
  • R e1 and R e2 are each independently selected from hydrogen, C 1 ⁇ C 20 linear alkyl, C 1 to C 20 branched alkyl, C 3 to C 20 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, and -C(R 1 )(R 2 ) Any one of (R 3 ).
  • R 1 and R 2 are each independently selected from C 1 ⁇ C 4 linear alkyl groups, C 1 ⁇ C 4 Any one of the branched chain alkyl group, C 3 ⁇ C 5 cycloalkyl group substituted C 1 ⁇ C 3 alkyl group, C 6 ⁇ C 12 aryl group substituted C 1 ⁇ C 3 alkyl group, Or R 1 and R 2 are connected to each other to form a C 3 -C 6 cycloalkyl group.
  • the Ar group in the above-mentioned photoinitiator may be an aryl group commonly used in the art.
  • the above-mentioned Ar is selected from substituted or unsubstituted phenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted thienylene and substituted Or any of the unsubstituted furanylene groups.
  • R 1 and R 2 are each independently selected from C 1 ⁇ C 4 linear alkyl groups, C 1 ⁇ C 4 branched chain alkyl groups, and phenyl substituted C 1 ⁇ C 3 Any one of the alkyl groups, R 3 is selected from any one of hydroxyl, alkoxy, N,N-dialkyl, N-morpholinyl, and N-thiomorpholinyl, R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are hydrogen, and R a2 is selected from hydrogen, C 1 ⁇ C 10 linear alkyl group, C 1 ⁇ C 10 branched chain Any one of an alkyl group and -COR e1 , R e1 is a C 1 to C 10 linear or branched alkyl group, a C 7 to C 10 aralkyl
  • the photoinitiator with the above structure has the advantages of good photoinitiation efficiency, non-migration and low odor.
  • the photoinitiator includes but is not limited to one or more of the following compounds:
  • the ethylenically unsaturated polymerized monomer for the ethylenic double bond used in the present application may be such a monomer commonly used in the prior art.
  • the ethylenically unsaturated polymerizable monomer of the ethylenic double bond is any type of acrylate compound, and the type of functional group of the acrylate compound is less than or equal to 3, which can be a monofunctional monomer or two or more Functional monomers.
  • the content of the above-mentioned ethylenic double bond coefficient unsaturated polymerized monomer can refer to the content of similar monomers in the prior art, preferably the weight percentage content of the ethylenically unsaturated polymerized monomer of the ethylenic double bond in the photocurable composition It is 10% to 85%, more preferably 20% to 65%.
  • the ethylenically unsaturated polymer oligomer used in the present application can also be selected from such materials commonly used in the prior art.
  • the ethylenically unsaturated polymer oligomer is selected from polyester acrylate, triacyl chloride Polyester acrylate, epoxy soybean oil acrylate, epoxy acrylate, modified epoxy acrylate, urethane acrylate, polybutadiene skeleton urethane (meth)acrylate, hydrogenated polybutadiene Carbamate (meth)acrylate of ene skeleton, urethane (meth)acrylate of polycarbonate skeleton, urethane (meth)acrylate of polyether skeleton, amino group of polyester skeleton Formate (meth)acrylate, isoprene-based (meth)acrylate, hydrogenated isoprene-based (meth)acrylate, epoxy (meth)acrylate, containing (meth)propylene Acyl acrylic polymer, (meth)acrylated
  • the dosage of the photoinitiator in the present application can also refer to the prior art.
  • the weight percentage of the photoinitiator is 0.5%-20%, preferably 2%-12%.
  • the above-mentioned photocurable composition further includes a coloring agent.
  • the amount of the colorant can be selected according to needs without affecting the photo-initiated polymerization.
  • the weight percentage of the colorant in the photocurable composition is 0.1%-30%, more preferably 1%-20%, to ensure Product application and efficient light-initiated polymerization.
  • the colorants used in this application include inorganic pigments and organic pigments.
  • the inorganic pigment may be: one or more of titanium white, chrome yellow, carbon black, ultramarine blue, iron blue, iron oxide red, and the like.
  • Organic pigments can be: Lake Red, Lithol Red, Hansa Yellow, Permanent Red, Diaryl Orange, Phthalocyanine Blue, Oleander Red, Diarylamine Yellow, Phthalocyanine Green, Benzidine Yellow, etc. One or more of.
  • additives may optionally be present in the above-mentioned photocurable composition to improve the properties and performance of the ink.
  • the additives include, but are not limited to, one or more of surfactants, stabilizers, wetting agents, dispersants, slip agents, rheology modifiers, defoamers, or storage enhancers.
  • the preparation method of the photocurable composition of the present invention includes the following steps: under the conditions of constant temperature and humidity, sanitation and cleanliness and avoiding ultraviolet radiation, it is completed through three steps of pre-dispersion of ingredients, rolling and grinding, and preparation. Mix the polymerizable compounds, initiators, colorants and additives with high-speed stirring to complete the pre-dispersion of ingredients; use the grinder-three-roller to disperse and grind the pre-dispersed materials to the specified particle size; then add low viscosity according to the specified viscosity Polymeric compound.
  • Another aspect of the application also provides a method for preparing the above-mentioned photoinitiator.
  • the preparation method includes: 1) Friedel-Crafts acylation reaction;
  • Intermediate b reacts with different raw materials c in the presence of a base to obtain intermediate c.
  • Intermediate c further reacts with raw material d to obtain intermediate d.
  • the reaction temperature of the hydrolysis reaction is 20-100° C., and limiting the temperature of the hydrolysis reaction within the above range is beneficial to increase the hydrolysis efficiency, thereby increasing the yield of the photoinitiator.
  • the above preparation method further includes adding a first organic solvent, an inorganic base and a phase transfer catalyst to the reaction system.
  • the addition of the first organic solvent is beneficial to improve the compatibility between the reaction raw materials, and the addition of the inorganic base and the phase transfer catalyst is beneficial to increase the reaction rate of the reaction and the yield of the photoinitiator.
  • the inorganic base is KOH and/or NaOH.
  • the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst.
  • the phase transfer catalyst includes but not limited to tetrabutylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium, trichloride One or more of the group consisting of ethylbenzylammonium and tetrabutylammonium hydrogen sulfate.
  • the type of solvent used is not particularly limited, as long as it can dissolve the raw materials and has no adverse effect on the reaction. Therefore, the first organic solvent can be a solvent commonly used in the art.
  • the first organic solvent includes but is not limited to one or more of the group consisting of dichloromethane, dichloroethane, benzene, xylene and acetonitrile.
  • the above-mentioned dehalogenation reaction may be carried out in the presence of a second organic solvent.
  • the second organic solvent includes but is not limited to one or more of the group consisting of dichloromethane, dichloroethane, benzene, xylene and acetonitrile;
  • reaction solution was slowly poured into 400 grams of ice water, the solids separated out, filtered under reduced pressure, the filter cake was slurried with methanol for 2 hours, filtered to obtain an off-white powdery solid wet product, and the wet product was dried in an oven at 50°C for 5 hours , To obtain 65 grams of off-white solid powder, with a yield of 91.2% and a purity of 99.1%.
  • the polyether modified polydimethylsiloxane BYK-371 comes from BYK Chemicals;
  • the cured composition was stirred under a yellow light, and then the material was taken and rolled onto a PET template to form a film, and dried at 80° C. for 3 minutes to obtain a coating film with a dry film thickness of 2 ⁇ m. Then, the coating film is cooled to room temperature and irradiated with a UV-LED lamp to expose the coating film to be cured into a film. The coating film is cured into a cured film to reach surface dryness through the evaluation of the number of crawler exposure belts, the more the number of passes, the less ideal the curing speed.
  • the light-curing composition is completely cured under the above-mentioned light-curing conditions, the sample is made into a film of the same size of 50*50mm, and the 50*50mm film is cut into 4 parts soaked in 50mL of 95% ethanol, 50°C, soaked for 2h, and taken The soaking liquid was analyzed by high performance liquid chromatography (HPLC). Measure the standard curve of each initiator, and calculate the corresponding concentration according to the peak area of the initiator in high performance liquid chromatography (HPLC), the unit is g/mL
  • the odor of the cured composition is judged by the nose, and the test results are divided into three levels: 1 (no odor), 2 (odor), and 3 (irritating odor)
  • the photocurable composition of the present invention is applied to different ink formulations and has the characteristics of fast curing speed, no migration, and low odor. It makes up for the shortcomings of the existing initiators and has good application prospects.
  • the compound represented by formula (I) of the present invention is used as a photoinitiator in the field of light curing, can exhibit excellent comprehensive application performance, and has broad application prospects.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
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Abstract

Disclosed in the present invention are a photoinitiator, a preparation method therefor and an application thereof, and a photocurable composition. The photoinitiator has the structure represented by formula (I). The photoinitiator of the present invention, the compound having structural formula I, has the features of high sensitivity, high molecular weight (MW>800), low odor, low migration, easy preparation, and low costs, and has strong absorption in the long-wavelength UV range of 365-405 nm, so that the photoinitiator can be well matched with a UV-LED light source. When the photoinitiator is applied to a photocurable composition, the advantages of low migration and long-wavelength initiation of the photoinitiator can be exerted. Therefore, the resulting photocurable ink product can be safely used in packaging materials of food, medicine, etc.

Description

光引发剂、其制备方法及应用、光固化组合物Photoinitiator, preparation method and application thereof, and photocurable composition 技术领域Technical field
本发明涉及光固化领域，具体而言，涉及一种光引发剂、其制备方法及应用、光固化组合物。The present invention relates to the field of photocuring, in particular to a photoinitiator, its preparation method and application, and a photocuring composition.
背景技术Background technique
UV固化技术由于具有固化时间短、速度快、节能、污染小等突出优点而成为当今社会关注的重点。传统UV固化使用的光源主要是高压汞灯，但是其具有能量效率低、发热量大、使用寿命较短、臭氧污染、含有重金属汞等缺陷，因此开发使用新的节能环保的固化光源大势所趋。UV-LED光源具有发光效率高、使用时间长、节能环保、放热量少等特点，克服了传统光源的缺点，收到了越来越多人的青睐，使之成为新型的UV固化方式。UV curing technology has become the focus of today's society due to its outstanding advantages such as short curing time, fast speed, energy saving, and low pollution. The light source used in traditional UV curing is mainly high-pressure mercury lamp, but it has the defects of low energy efficiency, large heat generation, short service life, ozone pollution, and heavy metal mercury. Therefore, the development and use of new energy-saving and environmentally friendly curing light sources is a general trend. UV-LED light source has the characteristics of high luminous efficiency, long use time, energy saving and environmental protection, and less heat. It overcomes the shortcomings of traditional light sources and is favored by more and more people, making it a new type of UV curing method.
与传统固化体系一样，UV-LED固化体系由低聚物、活性单体、光引发剂和助剂组成。其中光引发剂是固化体系的关键组分，对光固化的各种性能有着显著的影响。虽然UV-LED固化方式有着如上许多优势，但是UV-LED光源发射波长多为365nm以上，因此给传统光引发剂带来巨大挑战。Like the traditional curing system, the UV-LED curing system consists of oligomers, active monomers, photoinitiators and additives. Among them, the photoinitiator is the key component of the curing system, which has a significant impact on the various properties of light curing. Although the UV-LED curing method has many advantages as above, the UV-LED light source emits more than 365nm wavelength, which brings huge challenges to traditional photoinitiators.
目前，噻吨酮和酰基氧化膦是在此光谱区发生吸收的光引发剂。噻吨酮在曝光后容易发黄，这种黄变行为导致难以控制最终产品的色调。最重要的是，某些应用(主要是包装应用)优选不含噻吨酮的可辐射固化组合物。另一方面，酰基氧化磷产生中等挥发性的醛类降解产物，导致产生背景气味，这是包装应用中不可接受的。Currently, thioxanthone and acylphosphine oxide are photoinitiators that absorb in this spectral region. Thioxanthone is prone to yellowing after exposure, and this yellowing behavior makes it difficult to control the hue of the final product. Most importantly, radiation curable compositions that do not contain thioxanthone are preferred for certain applications (mainly packaging applications). On the other hand, acyl phosphorus oxide produces moderately volatile aldehyde degradation products, resulting in background odor, which is unacceptable in packaging applications.
同时，上述光引发剂主要为小分子引发剂，有迁移性风险，尤其在食品、医药等包装材料中可迁移残留物可能存在健康风险，因此需减少到最低限度。At the same time, the above-mentioned photoinitiators are mainly small-molecule initiators, which have a migration risk, especially in food, medicine and other packaging materials that may have a health risk, so they need to be reduced to a minimum.
发明内容Summary of the invention
本发明旨在提供一种光引发剂、其制备方法及应用、光固化组合物，以提供适用于UV-LED固化的多官能化α-氨基酮或α-羟基酮大分子光引发剂。The present invention aims to provide a photoinitiator, its preparation method and application, and a photocuring composition, so as to provide a multifunctional α-aminoketone or α-hydroxyketone macromolecular photoinitiator suitable for UV-LED curing.
为了实现上述目的，根据本发明的一个方面，提供了一种光引发剂。该光引发剂具有式(I)所示的结构：In order to achieve the above objective, according to one aspect of the present invention, a photoinitiator is provided. The photoinitiator has a structure represented by formula (I):
Figure PCTCN2020135471-appb-000001
Figure PCTCN2020135471-appb-000001
其中，R 1和R 2各自独立地选自C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 6～C 20的芳基取代的C 1～C 12的烷基和C 1～C 12的烷基取代的C 3～C 8的环烷基中的任意一种，R 1和R 2可彼此相连成环；R 3为光活性基团；两个Ar各自独立地选自取代或未被取代的亚芳基或取代或未被取代的亚杂芳基中的任意一种； Wherein, R 1 and R 2 are each independently selected from C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 cycloalkyl, C 3 ～C 8 Cycloalkyl substituted C 1 to C 12 alkyl, C 6 to C 20 aryl substituted C 1 to C 12 alkyl, and C 1 to C 12 alkyl substituted C 3 to C 8 ring Any of the alkyl groups, R 1 and R 2 can be connected to each other to form a ring; R 3 is a photoactive group; each of the two Ar is independently selected from substituted or unsubstituted arylene or substituted or unsubstituted Any one of the heteroarylene groups;
R a1、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基、-OR d1、-COR d1、-COOR d1、-SR d1、-SO 2R d1和-CONR d1R d2中的任意一种，其中R d1和R d2各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基和C 2～C 20的杂环基中的任意一种； R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are each independently selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 Branched chain alkyl group, C 3 ～C 20 cycloalkyl group, C 3 ～C 8 cycloalkyl group substituted C 1 ～C 12 alkyl group, C 1 ～C 12 alkyl group substituted C 3 ～C 8 Cycloalkyl group, C 7 ～C 20 aralkyl group, C 2 ～C 20 heterocyclic group, -OR d1 , -COR d1 , -COOR d1 , -SR d1 , -SO 2 R d1 and -CONR d1 Any one of R d2 , wherein R d1 and R d2 are each independently selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 ring Alkyl groups, C 1 ～C 12 alkyl groups substituted with C 3 ～C 8 cycloalkyl groups, C 3 ～C 8 cycloalkyl groups substituted with C 1 ～C 12 alkyl groups, C 7 ～C 20 aryl groups Any one of an alkyl group and a C 2 ～C 20 heterocyclic group;
R a2选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基、-NO 2、-OR e1、-COR e1、-COOR e1、-SR e1、-SO 2R e1和-CONR e1R e2中的任意一种，其中R e1和R e2各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基和-C(R 1)(R 2)(R 3)中的任意一种。 R a2 is selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 cycloalkyl, C 3 ～C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, -NO 2. Any one of -OR e1 , -COR e1 , -COOR e1 , -SR e1 , -SO 2 R e1 and -CONR e1 R e2 , wherein R e1 and R e2 are each independently selected from hydrogen, C 1 ~C 20 linear alkyl, C 1 to C 20 branched alkyl, C 3 to C 20 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, and -C(R 1 )(R 2 ) Any one of (R 3 ).
根据本发明的另一个方面，提供一种光固化组合物。该光固化组合物包括光引发剂、聚合单体和/或聚合低聚物，光引发剂包括上述任一种引发剂；优选的，所述聚合单体为烯属双键的烯属不饱和聚合单体，所述聚合低聚物为烯属不饱和聚合低聚物。According to another aspect of the present invention, a photocurable composition is provided. The photocurable composition includes a photoinitiator, a polymerized monomer and/or a polymerized oligomer, and the photoinitiator includes any of the above-mentioned initiators; preferably, the polymerized monomer is an ethylenically unsaturated olefinic double bond Polymeric monomers, and the polymerized oligomers are ethylenically unsaturated polymerized oligomers.
根据本发明的另一方面，提供了一种光固化油墨，包括光固化组合物，该光固化组合物选自上述任一种的光固化组合物中的任意一种。According to another aspect of the present invention, there is provided a photocurable ink including a photocurable composition selected from any one of the above-mentioned photocurable compositions.
根据本发明的再一个方面，提供一种光引发剂在光固化领域中的应用；优选的，光固化领域为UV-LED光源的光固化领域。According to another aspect of the present invention, an application of a photoinitiator in the field of light curing is provided; preferably, the field of light curing is the field of light curing of UV-LED light sources.
根据本发明的又一个方面，提供一种光引发剂的制备方法。该制备方法包括以下步骤：According to another aspect of the present invention, a method for preparing a photoinitiator is provided. The preparation method includes the following steps:
1)原料a和原料b傅克酰基化反应得到中间体a；1) Friedel-Crafts acylation reaction of raw material a and raw material b to obtain intermediate a;
Figure PCTCN2020135471-appb-000002
Figure PCTCN2020135471-appb-000002
2)中间体a发生脱水反应得到中间体b；2) Intermediate a undergoes dehydration reaction to obtain intermediate b;
Figure PCTCN2020135471-appb-000003
Figure PCTCN2020135471-appb-000003
3)中间体b和原料c发生取代反应得到中间体c；3) Intermediate b and raw material c undergo a substitution reaction to obtain intermediate c;
Figure PCTCN2020135471-appb-000004
Figure PCTCN2020135471-appb-000004
4)中间体c与原料d发生傅克酰基化反应，得到中间体d；4) Friedel-Crafts acylation reaction between intermediate c and raw material d to obtain intermediate d;
Figure PCTCN2020135471-appb-000005
Figure PCTCN2020135471-appb-000005
5)中间体d发生取代反应，得到光引发剂5) Intermediate d undergoes substitution reaction to obtain photoinitiator
Figure PCTCN2020135471-appb-000006
Figure PCTCN2020135471-appb-000006
应用本发明的技术方案，具有上述结构式I的化合物具有高感度、高分子量(MW>800)、低气味、低迁移、易制备、低成本的特点，且在365～405nm的长波长UV范围内具有较强的吸收，能够与UV-LED光源很好的匹配。将其应用于光固化组合物中时，其低迁移性、长波长引发的优势得以发挥，因此由此得到光固化油墨产品可安全应用于食品、医药等包装材料中。Applying the technical solution of the present invention, the compound with the above structural formula I has the characteristics of high sensitivity, high molecular weight (MW>800), low odor, low migration, easy preparation, low cost, and is within the long wavelength UV range of 365-405nm It has strong absorption and can be well matched with UV-LED light source. When it is applied to a photocurable composition, its advantages of low migration and long-wavelength initiation can be brought into play. Therefore, the resulting photocurable ink product can be safely used in packaging materials such as food and medicine.
具体实施方式Detailed ways
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。It should be noted that the embodiments in the application and the features in the embodiments can be combined with each other if there is no conflict. The present invention will be described in detail below in conjunction with embodiments.
如本申请背景技术所分析的，现有技术的光引发剂主要为小分子引发剂，有迁移性风险，尤其在食品、医药等包装材料中可迁移残留物可能存在健康风险。为了解决该问题，本申请提供了光固化组合物、光固化油墨。As analyzed in the background art of this application, the photoinitiators in the prior art are mainly small molecule initiators, which have a migration risk, and especially the migration of residues in packaging materials such as food and medicine may have a health risk. In order to solve this problem, the present application provides a photocurable composition and a photocurable ink.
根据本发明一种典型的实施方式，提供一种光引发剂。该光引发剂具有式(I)所示的结构：According to a typical embodiment of the present invention, a photoinitiator is provided. The photoinitiator has a structure represented by formula (I):
Figure PCTCN2020135471-appb-000007
Figure PCTCN2020135471-appb-000007
其中，R 1和R 2各自独立地选自C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 6～C 20的芳基取代的C 1～C 12的烷基和C 1～C 12的烷基取代的C 3～C 8的环烷基中的任意一种，R 1和R 2可彼此相连成环；R 3为光活性基团；两个Ar各自独立地选自取代或未被取代的亚芳基或取代或未被取代的亚杂芳基中的任意一种； Wherein, R 1 and R 2 are each independently selected from C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 cycloalkyl, C 3 ～C 8 Cycloalkyl substituted C 1 to C 12 alkyl, C 6 to C 20 aryl substituted C 1 to C 12 alkyl, and C 1 to C 12 alkyl substituted C 3 to C 8 ring Any of the alkyl groups, R 1 and R 2 can be connected to each other to form a ring; R 3 is a photoactive group; each of the two Ar is independently selected from substituted or unsubstituted arylene or substituted or unsubstituted Any one of the heteroarylene groups;
R a1、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基、-OR d1、-COR d1、-COOR d1、-SR d1、-SO 2R d1和-CONR d1R d2中的任意一种，其中R d1和R d2各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基和C 2～C 20的杂环基中的任意一种； R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are each independently selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 Branched chain alkyl group, C 3 ～C 20 cycloalkyl group, C 3 ～C 8 cycloalkyl group substituted C 1 ～C 12 alkyl group, C 1 ～C 12 alkyl group substituted C 3 ～C 8 Cycloalkyl group, C 7 ～C 20 aralkyl group, C 2 ～C 20 heterocyclic group, -OR d1 , -COR d1 , -COOR d1 , -SR d1 , -SO 2 R d1 and -CONR d1 Any one of R d2 , wherein R d1 and R d2 are each independently selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 ring Alkyl groups, C 1 ～C 12 alkyl groups substituted with C 3 ～C 8 cycloalkyl groups, C 3 ～C 8 cycloalkyl groups substituted with C 1 ～C 12 alkyl groups, C 7 ～C 20 aryl groups Any one of alkyl group and C 2 ～C 20 heterocyclic group;
R a2选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基、-NO 2、-OR e1、-COR e1、-COOR e1、-SR e1、-SO 2R e1和-CONR e1R e2中的任意一种，其中R e1和R e2各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基和-C(R 1)(R 2)(R 3)中的任意一种。 R a2 is selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 cycloalkyl, C 3 ～C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, -NO 2. Any one of -OR e1 , -COR e1 , -COOR e1 , -SR e1 , -SO 2 R e1 and -CONR e1 R e2 , wherein R e1 and R e2 are each independently selected from hydrogen, C 1 ~C 20 linear alkyl, C 1 to C 20 branched alkyl, C 3 to C 20 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, and -C(R 1 )(R 2 ) Any one of (R 3 ).
本发明的具有上述结构式I的化合物具有高感度、高分子量(MW>800)、低气味、低迁移、易制备、低成本的特点，且在365～405nm的长波长UV范围内具有较强的吸收，能够与UV-LED光源很好的匹配。将其应用于光固化组合物中时，其低迁移性、长波长引发的优势得以发挥，因此由此得到光固化油墨产品可安全应用于食品、医药等包装材料中。The compound of the above-mentioned structural formula I of the present invention has the characteristics of high sensitivity, high molecular weight (MW>800), low odor, low migration, easy preparation, low cost, and has a strong UV range in the long-wavelength UV range from 365 to 405 nm. Absorption, which can be well matched with UV-LED light source. When it is applied to a photocurable composition, its advantages of low migration and long-wavelength initiation can be brought into play. Therefore, the resulting photocurable ink product can be safely used in packaging materials such as food and medicine.
本申请的上述化合物中，R 3为光活性基团，现有技术中常用的光活性基团可以考虑应用于本申请中，优选地上述R 3选自羟基、烷氧基、N，N-二烷基、N-吗啉基、N-硫代吗啉基和N-取代哌嗪基中的任意一种。以实现对长波UV的更强吸收。 In the above-mentioned compounds of the present application, R 3 is a photoactive group. The photoactive groups commonly used in the prior art can be considered for use in this application. Preferably, the above R 3 is selected from the group consisting of hydroxyl, alkoxy, N, N- Any one of dialkyl, N-morpholinyl, N-thiomorpholinyl and N-substituted piperazinyl. In order to achieve stronger absorption of long-wave UV.
为了进一步提高上述光引发剂的综合性能，可以对式(I)中的取代基进行优选。In order to further improve the overall performance of the above-mentioned photoinitiator, the substituents in formula (I) may be preferred.
为了提高上述结构式I的结构稳定性以及制备的方便性，在一种优选的实施例中，R 1和R 2各自独立地选自C 1～C 4的直链烷基、C 1～C 4的支链烷基、C 3～C 5的环烷基取代的C 1～C 3的烷基、C 6～C 12的芳基取代的C 1～C 3的烷基中的任意一种，或者R 1和R 2彼此相连形成C 3～C 6的环烷基。 In order to improve the structural stability of the above structural formula I and the convenience of preparation, in a preferred embodiment, R 1 and R 2 are each independently selected from C 1 ～C 4 linear alkyl groups, C 1 ～C 4 Any one of the branched chain alkyl group, C 3 ～C 5 cycloalkyl group substituted C 1 ～C 3 alkyl group, C 6 ～C 12 aryl group substituted C 1 ～C 3 alkyl group, Or R 1 and R 2 are connected to each other to form a C 3 -C 6 cycloalkyl group.
上述光引发剂中Ar基团可以是本领域常用的芳基基团。为了进一步降低上述化合物的迁移率，同时提高其感度和光引发活性，优选上述Ar选自取代或未取代的亚苯基、取代或未取代的亚吡啶基、取代或未取代的亚噻吩基和取代或未取代的亚呋喃基中的任意一种。The Ar group in the above-mentioned photoinitiator may be an aryl group commonly used in the art. In order to further reduce the mobility of the above-mentioned compounds, and at the same time increase its sensitivity and photoinitiation activity, it is preferred that the above-mentioned Ar is selected from substituted or unsubstituted phenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted thienylene and substituted Or any of the unsubstituted furanylene groups.
为了进一步降低迁移性，优选上述R a2选自氢、C 1～C 10的直链烷基、C 1～C 10的支链烷基、C 7～C 10的芳烷基、C 2～C 10的杂环基、-NO 2、-OR e1、-COR e1、-COOR e1或-CONR e1R e2，其中R e1和R e2各自独立地表示氢、C 1～C 10的直链烷基、C 1～C 10的支链烷基、C 3～C 10的环烷基、C 3～C 8的环烷基取代的C 1～C 5的烷基、C 1～C 5的烷基取代的C 3～C 8的环烷基、C 7～C 10的芳烷基、C 2～C 20的杂环基和-C(R 1)(R 2)(R 3)中的任意一种。 In order to further reduce mobility, it is preferable that the above-mentioned Ra2 is selected from hydrogen, C 1 to C 10 linear alkyl, C 1 to C 10 branched alkyl, C 7 to C 10 aralkyl, C 2 to C The heterocyclic group of 10 , -NO 2 , -OR e1 , -COR e1 , -COOR e1 or -CONR e1 R e2 , wherein R e1 and R e2 each independently represent hydrogen, a C 1 ～C 10 linear alkyl group , C 1 ～C 10 branched alkyl, C 3 ～C 10 cycloalkyl, C 3 ～C 8 cycloalkyl substituted C 1 ～C 5 alkyl, C 1 ～C 5 alkyl Any one of substituted C 3 to C 8 cycloalkyl, C 7 to C 10 aralkyl, C 2 to C 20 heterocyclic group, and -C(R 1 )(R 2 )(R 3) Kind.
在一种实施例中，优选上述R 1和R 2各自独立地选自C 1～C 4的直链烷基、C 1～C 4的支链烷基、苯基取代的C 1～C 3的烷基中的任意一种，R 3选自羟基、烷氧基、N，N-二烷基、N-吗啉基、N-硫代吗啉基中的任意一种，R a1、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4为氢，R a2选自氢、C 1～C 10的直链烷基、C 1～C 10的支链烷基和-COR e1中的任意一种，R e1为C 1～C 10的直链或支链烷基、C 7～C 10的芳烷基、C 2～C 20的杂芳基和-C(R 1)(R 2)(R 3)中的任意一种。 In an embodiment, it is preferred that the above-mentioned R 1 and R 2 are each independently selected from C 1 ～C 4 linear alkyl groups, C 1 ～C 4 branched chain alkyl groups, and phenyl substituted C 1 ～C 3 Any one of the alkyl groups, R 3 is selected from any one of hydroxyl, alkoxy, N,N-dialkyl, N-morpholinyl, and N-thiomorpholinyl, R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are hydrogen, and R a2 is selected from hydrogen, C 1 ～C 10 linear alkyl group, C 1 ～C 10 branched chain Any one of an alkyl group and -COR e1 , R e1 is a C 1 to C 10 linear or branched alkyl group, a C 7 to C 10 aralkyl group, a C 2 to C 20 heteroaryl group, and- Any of C(R 1 )(R 2 )(R 3 ).
在另一种实施例中，上述R 1和R 2彼此相连形成C 3～C 6的环烷基，R 3为羟基或烷氧基，R a1、R a2、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4为氢。 In another embodiment, the above-mentioned R 1 and R 2 are connected to each other to form a C 3 ～C 6 cycloalkyl group, R 3 is a hydroxyl group or an alkoxy group, Ra1 , Ra2 , Ra3 , Ra4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are hydrogen.
具有上述结构的光引发剂具有良好的光引发效率、不易迁移和气味低等优点。在一种优选的实施例中，光引发剂包括但不限于以下化合物中的一种或多种：The photoinitiator with the above structure has the advantages of good photoinitiation efficiency, non-migration and low odor. In a preferred embodiment, the photoinitiator includes but is not limited to one or more of the following compounds:
Figure PCTCN2020135471-appb-000008
Figure PCTCN2020135471-appb-000008
Figure PCTCN2020135471-appb-000009
Figure PCTCN2020135471-appb-000009
Figure PCTCN2020135471-appb-000010
Figure PCTCN2020135471-appb-000010
Figure PCTCN2020135471-appb-000011
Figure PCTCN2020135471-appb-000011
用于本申请的烯属双键的烯属不饱和聚合单体可以为现有技术中常用的此类单体。优选该烯属双键的烯属不饱和聚合单体为任意一种丙烯酸酯类化合物，且丙烯酸酯类化合物的官能团种类小于等于3，可为单官能团单体也可为两个及两个以上官能团的单体。The ethylenically unsaturated polymerized monomer for the ethylenic double bond used in the present application may be such a monomer commonly used in the prior art. Preferably, the ethylenically unsaturated polymerizable monomer of the ethylenic double bond is any type of acrylate compound, and the type of functional group of the acrylate compound is less than or equal to 3, which can be a monofunctional monomer or two or more Functional monomers.
示例性地，单官能团单体可以为：丙烯酸异戊酯、丙烯酸硬脂基酯、丙烯酸月桂基酯、丙烯酸辛酯、丙烯酸癸酯、丙烯酸异戊基苯乙烯酯、丙烯酸异硬脂基酯、丙烯酸2-乙基己基-二甘醇酯、丙烯酸2-羟基丁酯、2-丙烯酰氧基乙基六氢邻苯二甲酸、丙烯酸丁氧基乙酯、丙烯酸乙氧基二甘醇酯、丙烯酸甲氧基二甘醇酯、丙烯酸甲氧基聚乙二醇酯、丙烯酸甲氧基丙二醇酯、丙烯酸苯氧基乙酯、丙烯酸四氢化糠酯、丙烯酸异冰片基酯、丙烯酸2-羟乙酯、丙烯酸2-羟丙酯、丙烯酸2-羟基-3-苯氧基丙酯、乙烯基醚丙烯酸酯、2-丙烯酰氧基乙基丁二酸、2-丙烯酰氧基乙基邻苯二甲酸、2-丙烯酰氧基乙基-2-羟乙基-邻苯二甲酸、和丙烯酸叔丁基环己酯、二丙烯酸三甘醇酯、二丙烯酸四甘醇酯、二丙烯酸聚乙二醇酯、二丙烯酸二丙二醇酯、二丙烯酸三丙二醇酯、二丙烯酸聚丙二醇酯、二丙烯酸1,4-丁二醇酯、二丙烯酸1,6-己二醇酯、二丙烯酸1,9-壬二醇酯、二丙烯酸新戊二醇酯、二甲醇-三环癸烷二丙烯酸酯、羟基新戊酸酯二丙烯酸新戊二醇酯、三羟甲基丙烷三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三丙烯酸三(丙二醇)酯、己内酯改性的三羟甲基丙烷三丙烯酸酯、三丙烯酸季戊四醇酯、四丙烯酸季戊四醇酯、四丙烯酸季戊四醇乙氧基酯、六丙烯酸二季戊四醇酯、二三羟甲基丙烷四丙烯酸酯、三丙烯酸丙三醇丙氧基酯和己内酰胺改性的六丙烯酸二季戊四醇酯，或N-乙烯基酰胺，例如N-乙烯基己内酰胺或N-乙烯基甲酰胺；或丙烯酰胺或取代的丙烯酰胺，例如丙烯酰基吗啉；其它合适的单官能丙烯酸酯包括己内酯丙烯酸酯、环状三羟甲基丙烷缩甲醛丙烯酸酯、乙氧基化壬基苯酚丙烯酸酯、丙烯酸异癸酯、丙烯酸异辛酯、丙烯酸辛癸酯、烷氧基化苯酚丙烯酸酯、丙烯酸十三烷基酯和烷氧基化环己酮二甲醇二丙烯酸酯。Exemplarily, the monofunctional monomer may be: isoamyl acrylate, stearyl acrylate, lauryl acrylate, octyl acrylate, decyl acrylate, isoamyl styrene acrylate, isostearyl acrylate, 2-ethylhexyl-diethylene glycol acrylate, 2-hydroxybutyl acrylate, 2-acryloxyethylhexahydrophthalic acid, butoxyethyl acrylate, ethoxydiglycol acrylate, Methoxydiethylene glycol acrylate, methoxypolyethylene glycol acrylate, methoxypropylene glycol acrylate, phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate Ester, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, vinyl ether acrylate, 2-acryloxyethyl succinic acid, 2-acryloxyethyl o-benzene Dicarboxylic acid, 2-acryloxyethyl-2-hydroxyethyl-phthalic acid, and tert-butyl cyclohexyl acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate Ester, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonane diacrylate Alcohol ester, neopentyl glycol diacrylate, dimethanol-tricyclodecane diacrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate Acrylate, triacrylate tri(propylene glycol), caprolactone modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetraacrylate ethoxy ester, dipentaerythritol hexaacrylate, Ditrimethylolpropane tetraacrylate, glycerol propoxy triacrylate, and caprolactam-modified dipentaerythritol hexaacrylate, or N-vinylamide, such as N-vinylcaprolactam or N-vinylformamide ; Or acrylamide or substituted acrylamide, such as acryloylmorpholine; other suitable monofunctional acrylates include caprolactone acrylate, cyclic trimethylolpropane formal acrylate, ethoxylated nonylphenol acrylate Esters, isodecyl acrylate, isooctyl acrylate, octyldecyl acrylate, alkoxylated phenol acrylate, tridecyl acrylate, and alkoxylated cyclohexanone dimethanol diacrylate.
示例性地，上述两个及两个以上官能团的单体可以为：氧基化环己酮二甲醇二丙烯酸酯、烷氧基化己二醇二丙烯酸酯、二烷二醇二丙烯酸酯、二烷二醇二丙烯酸酯、环己酮二甲醇二丙烯酸酯、二丙烯酸二甘醇酯、二缩三丙二醇二丙烯酸酯、丙氧基化丙三醇三丙烯酸酯、丙氧基化三羟甲基丙烷三丙烯酸酯、双季戊四醇五丙烯酸酯、二-三羟甲基丙烷四丙烯酸酯、二季戊四醇五丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯、甲氧基化二醇丙烯酸酯、丙氧基化的二丙烯酸新戊二醇酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二丙烯酸1,3-丁二醇酯、二甲基丙烯酸1,3-丁二醇酯、二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯、烷氧基化的脂肪族二丙烯酸酯、乙氧基化三羟甲基丙烷三丙烯酸酯、二丙烯酸二乙二醇酯、二甲基丙烯酸二乙二醇酯、二丙烯酸二丙二醇酯、二丙烯酸三丙二醇酯、二甲基丙烯酸三乙二醇酯、烷氧基化的二丙烯酸己二醇酯。Exemplarily, the above two or more functional group monomers can be: oxylated cyclohexanone dimethanol diacrylate, alkoxylated hexanediol diacrylate, dialkylene glycol diacrylate, dialkylene glycol diacrylate, Alkyl glycol diacrylate, cyclohexanone dimethanol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, propoxylated glycerol triacrylate, propoxylated trimethylol Propane triacrylate, dipentaerythritol pentaacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated pentaerythritol pentaacrylate, methoxylated glycol acrylate, propoxylated Neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,3-butanediol diacrylate, 1,6-hexanediol dimethacrylate, 3-butanediol ester, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, alkoxylated aliphatic diacrylate, ethoxylated trimethylol Propane triacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, alkoxylated Hexanediol diacrylate.
上述烯属双键的系数不饱和聚合单体的含量可以参考现有技术中类似单体的含量，优选该光固化组合物中烯属双键的烯属不饱和聚合单体的重量百分含量为10％～85％，更优选为20％～65％。The content of the above-mentioned ethylenic double bond coefficient unsaturated polymerized monomer can refer to the content of similar monomers in the prior art, preferably the weight percentage content of the ethylenically unsaturated polymerized monomer of the ethylenic double bond in the photocurable composition It is 10% to 85%, more preferably 20% to 65%.
用于本申请的烯属不饱和聚合物低聚物也可以从现有技术中常用的该类物质中进行选择，优选该烯属不饱和聚合低聚物选自聚酯丙烯酸酯、三官氯化聚酯丙烯酸酯、环氧大豆油丙烯酸酯、环氧丙烯酸酯、改性环氧丙烯酸酯、聚氨酯丙烯酸酯、聚丁二烯骨架的氨基甲酸酯(甲基)丙烯酸酯、氢化聚丁二烯骨架的氨基甲酸酯(甲基)丙烯酸酯、聚碳酸酯骨架的氨基甲酸酯(甲基)丙烯酸酯、聚醚骨架的氨基甲酸酯(甲基)丙烯酸酯、聚酯骨架的氨基甲酸酯(甲基) 丙烯酸酯、异戊二烯系(甲基)丙烯酸酯、氢化异戊二烯系(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、含有(甲基)丙烯酰基的丙烯酸聚合物、(甲基)丙烯酸酯化的环氧树脂、(甲基)丙烯酸酯化的聚酯、(甲基)丙烯酸酯化的聚氨酯、(甲基)丙烯酸酯化的聚醚、含乙烯基醚或含环氧基团的聚酯、含乙烯基醚或含环氧基团的聚氨酯和含乙烯基醚或含环氧基团的聚醚中的任意一种多种。优选光固化组合物中烯属不饱和聚合低聚物的重量百分含量为5％～60％，更优选为10％～55％。The ethylenically unsaturated polymer oligomer used in the present application can also be selected from such materials commonly used in the prior art. Preferably, the ethylenically unsaturated polymer oligomer is selected from polyester acrylate, triacyl chloride Polyester acrylate, epoxy soybean oil acrylate, epoxy acrylate, modified epoxy acrylate, urethane acrylate, polybutadiene skeleton urethane (meth)acrylate, hydrogenated polybutadiene Carbamate (meth)acrylate of ene skeleton, urethane (meth)acrylate of polycarbonate skeleton, urethane (meth)acrylate of polyether skeleton, amino group of polyester skeleton Formate (meth)acrylate, isoprene-based (meth)acrylate, hydrogenated isoprene-based (meth)acrylate, epoxy (meth)acrylate, containing (meth)propylene Acyl acrylic polymer, (meth)acrylated epoxy resin, (meth)acrylated polyester, (meth)acrylated polyurethane, (meth)acrylated polyether, Any one or more of vinyl ether or epoxy group-containing polyester, vinyl ether or epoxy group-containing polyurethane, and vinyl ether or epoxy group-containing polyether. Preferably, the weight percentage of the ethylenically unsaturated polymerized oligomer in the photocurable composition is 5% to 60%, more preferably 10% to 55%.
本申请的光引发剂的用量同样可以参考现有技术，优选该光引发剂的重量百分含量为0.5％～20％，优选为2％～12％。The dosage of the photoinitiator in the present application can also refer to the prior art. Preferably, the weight percentage of the photoinitiator is 0.5%-20%, preferably 2%-12%.
在某些情况下，使用两种或更多种以上所述引发剂的混合物是有利的。因此，本申请上述化合物也可以与已知的其他光引发剂混合使用。例如：樟脑醌，二苯甲酮类化合物(如二苯甲酮(BP)、2,4,6-三甲基二苯甲酮和2-甲基二苯甲酮)，α-羟基酮类化合物(如2-羟基-2-甲基-1-苯基-丙酮(1173)和1-羟基-环己基-苯基-酮(184))，α-胺基酮类化合物(如(4-甲硫基苯甲酰基)-1-甲基-1-吗啉代乙烷(907)和(4-吗啉代苯甲酰基)-1-苄基-1-二甲基氨基丙烷(369))，酰基膦氧化物(如(2,4,6-三甲基-苯甲酰基)二苯基氧化膦(TPO)和双(2,4,6-三甲基苯甲酰基)-苯基氧化膦(819))，安息香醚类化合物(如安息香双甲醚和安息香异丙醚)，苯偶酰衍生物(如I-651)，肟酯类化合物(如如1,2-辛二酮-1-[4-(苯硫基)苯基]-2-(4-苯甲酰基肟)(OXE01)和乙酮1-[9-乙基-6-(2-甲基苯甲酰基)-9H-咔唑-3-基]-1-(4-乙酰基肟)(OXE02))，三嗪类化合物(如三嗪B和三嗪D)，FMT(784)，以及硫杂蒽酮类化合物(如异丙基硫杂蒽(ITX)和2-氯硫杂蒽酮(CTX))。In some cases, it is advantageous to use a mixture of two or more of the above-mentioned initiators. Therefore, the above-mentioned compounds of this application can also be used in combination with other known photoinitiators. For example: camphorquinone, benzophenone compounds (such as benzophenone (BP), 2,4,6-trimethylbenzophenone and 2-methylbenzophenone), α-hydroxyketones Compounds (such as 2-hydroxy-2-methyl-1-phenyl-acetone (1173) and 1-hydroxy-cyclohexyl-phenyl-ketone (184)), α-amino ketone compounds (such as (4- (Methylthiobenzoyl)-1-methyl-1-morpholinoethane (907) and (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (369) ), acylphosphine oxides (such as (2,4,6-trimethyl-benzoyl) diphenylphosphine oxide (TPO) and bis(2,4,6-trimethylbenzoyl)-phenyl Phosphine oxide (819)), benzoin ether compounds (such as benzoin dimethyl ether and isopropyl benzoin), benzyl derivatives (such as I-651), oxime ester compounds (such as 1,2-octanedione) -1-[4-(phenylthio)phenyl]-2-(4-benzoyl oxime) (OXE01) and ethyl ketone 1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-1-(4-acetyloxime) (OXE02)), triazine compounds (such as triazine B and triazine D), FMT (784), and thioxanthone Compounds (such as isopropylthioxanthone (ITX) and 2-chlorothioxanthone (CTX)).
在需要制备着色产品时，优选上述光固化组合物还包括着色剂。着色剂的用量可以根据需要在不影响光引发聚合的基础上进行选择，优选光固化组合物中着色剂的重量百分含量为0.1％～30％，更优选为1％～20％，以保证产品应用和高效光引发聚合。When it is necessary to prepare a colored product, it is preferable that the above-mentioned photocurable composition further includes a coloring agent. The amount of the colorant can be selected according to needs without affecting the photo-initiated polymerization. Preferably, the weight percentage of the colorant in the photocurable composition is 0.1%-30%, more preferably 1%-20%, to ensure Product application and efficient light-initiated polymerization.
用于本申请的着色剂包括无机颜料和有机颜料两大类。The colorants used in this application include inorganic pigments and organic pigments.
示例性地，无机颜料可以为：钛白、铬黄、炭黑、群青、铁蓝、氧化铁红等中的一种或多种。有机颜料可以为：色淀红、立索尔宝红、汉沙黄、永固红、二芳基橙、酞菁蓝、夹竹桃红、二芳胺黄、酞菁绿、联苯胺黄等中的一种或多种。Exemplarily, the inorganic pigment may be: one or more of titanium white, chrome yellow, carbon black, ultramarine blue, iron blue, iron oxide red, and the like. Organic pigments can be: Lake Red, Lithol Red, Hansa Yellow, Permanent Red, Diaryl Orange, Phthalocyanine Blue, Oleander Red, Diarylamine Yellow, Phthalocyanine Green, Benzidine Yellow, etc. One or more of.
根据不同应用的需求，上述光固化组合物中可任选地存在其它组分或添加剂，以改善油墨的性质和性能。添加剂包括但不限于表面活性剂、稳定剂、润湿剂、分散剂、爽滑剂、流变改性剂、消泡剂或储存增强剂中的一种或多种。According to the requirements of different applications, other components or additives may optionally be present in the above-mentioned photocurable composition to improve the properties and performance of the ink. The additives include, but are not limited to, one or more of surfactants, stabilizers, wetting agents, dispersants, slip agents, rheology modifiers, defoamers, or storage enhancers.
本发明的光固化组合物的制备方法包括如下步骤：在恒温恒湿、卫生洁净和避免紫外线照射的条件下通过配料预分散、轧制研磨、调制三个环节完成。将聚合性化合物、引发剂、着色剂份及助剂混合高速搅拌完成配料预分散；将预分散好物料用研磨机——三辊机联机分散研磨至规定粒径；再根据规定黏度加入低粘度聚合性化合物。The preparation method of the photocurable composition of the present invention includes the following steps: under the conditions of constant temperature and humidity, sanitation and cleanliness and avoiding ultraviolet radiation, it is completed through three steps of pre-dispersion of ingredients, rolling and grinding, and preparation. Mix the polymerizable compounds, initiators, colorants and additives with high-speed stirring to complete the pre-dispersion of ingredients; use the grinder-three-roller to disperse and grind the pre-dispersed materials to the specified particle size; then add low viscosity according to the specified viscosity Polymeric compound.
根据本发明的另一方面，提供了一种光固化油墨，包括光固化组合物，该光固化组合物选自上述任一种的光固化组合物中的任意一种。According to another aspect of the present invention, there is provided a photocurable ink including a photocurable composition selected from any one of the above-mentioned photocurable compositions.
由于本发明的具有上述结构式I的化合物具有高感度、高分子量(MW>800)、低气味、低迁移、易制备、低成本的特点，且在365～405nm的长波长UV范围内具有较强的吸收，能够与UV-LED光源很好的匹配。将其应用于光固化组合物作为油墨使用时，其低迁移性、长波长引发的优势得以发挥，因此由此得到光固化油墨产品可安全应用于食品、医药等包装材料中。Because the compound of the above-mentioned structural formula I of the present invention has the characteristics of high sensitivity, high molecular weight (MW>800), low odor, low migration, easy preparation, and low cost, and has a strong UV in the long-wavelength UV range of 365-405nm. The absorption can be well matched with UV-LED light source. When it is applied to a photocurable composition as an ink, its advantages of low migration and long-wavelength initiation can be brought into play. Therefore, the resulting photocurable ink product can be safely used in packaging materials such as food and medicine.
根据本发明一种典型的实施方式，提供上述、光引发剂在光固化领域中的应用；优选的，光固化领域为UV-LED光源的光固化领域。According to a typical embodiment of the present invention, the application of the above-mentioned photoinitiator in the field of light curing is provided; preferably, the field of light curing is the field of light curing of UV-LED light sources.
本申请的另一方面还提供了一种上述光引发剂的制备方法。该制备方法包括：1)傅克酰基化反应；Another aspect of the application also provides a method for preparing the above-mentioned photoinitiator. The preparation method includes: 1) Friedel-Crafts acylation reaction;
Figure PCTCN2020135471-appb-000012
Figure PCTCN2020135471-appb-000012
在三氯化铝存在条件下，原料a与不同的酸酐原料b进行傅克酰基化反应，得到中间体a；In the presence of aluminum trichloride, raw material a is subjected to Friedel-Crafts acylation with different acid anhydride raw materials b to obtain intermediate a;
2)脱水反应2) Dehydration reaction
Figure PCTCN2020135471-appb-000013
Figure PCTCN2020135471-appb-000013
在多聚磷酸存在下，高温加热脱水，得到中间体b。In the presence of polyphosphoric acid, heat dehydration at high temperature to obtain intermediate b.
3)取代反应3) Substitution reaction
Figure PCTCN2020135471-appb-000014
Figure PCTCN2020135471-appb-000014
中间体b在碱存在下与不同的原料c反应得到中间体c。Intermediate b reacts with different raw materials c in the presence of a base to obtain intermediate c.
4)傅克酰基化反应4) Friedel-Crafts acylation reaction
Figure PCTCN2020135471-appb-000015
Figure PCTCN2020135471-appb-000015
中间体c进一步与原料d反应，得到中间体d。Intermediate c further reacts with raw material d to obtain intermediate d.
5)取代反应5) Substitution reaction
Figure PCTCN2020135471-appb-000016
Figure PCTCN2020135471-appb-000016
中间体d能够通过水解反应或与含非羟基光活性基团的化合物进行取代脱卤反应，引入光活性基团，从而形成所需的光引发剂。The intermediate d can introduce a photoactive group through a hydrolysis reaction or a substitution dehalogenation reaction with a compound containing a non-hydroxyl photoactive group to form the required photoinitiator.
上述制备方法中，使用的原料均是现有技术中的已知化合物，可通过商业购得或者经已知的合成方法简便地制备而成。为了进一步提高傅克酰基化反应效率，优选地，傅克酰基化反应的反应温度为-10～10℃；为了提高脱水反应的效率，优选地，脱水反应的反应温度为100～140℃；步骤3)取代反应在碱性条件下进行；步骤4)傅克酰基化反应温度为-5-30℃；步骤5)在一种优选的实施方式中，中间体d通过水解反应，得到化合物，通过水解反应，可以在中间体d中引入羟基或烷氧基。优选地，水解反应的反应温度为20～100℃，将水解反应的温度限定在上述范围内有利于提高水解效率，进而提高光引发剂的收率。优选地，在进行水解反应之前，上述制备方法还包括向反应体系中加入第一有机溶剂、无机碱和相转移催化剂。加入第一有机溶剂有利于提高各反应原料之间的相溶性，无机碱和相转移催化剂的加入有利于提高该反应的反应速率以及光引发剂的收率。更优选地，无机碱为KOH和/或NaOH。更优选地，相转移催化剂为季铵盐类相转移催化剂，进一步优选地，相转移催化剂包括但不限于四丁基溴化铵、四丙基溴化铵、四正丁基铵、氯化三乙基苄基铵和硫酸氢四丁基铵组成的组中的一种或多种。In the above preparation methods, the raw materials used are all known compounds in the prior art, which can be purchased commercially or simply prepared by known synthetic methods. In order to further improve the efficiency of the Friedel-Crafts acylation reaction, preferably, the reaction temperature of the Friedel-Crafts acylation reaction is -10 to 10°C; in order to improve the efficiency of the dehydration reaction, preferably, the reaction temperature of the dehydration reaction is 100 to 140°C; 3) The substitution reaction is carried out under alkaline conditions; Step 4) Friedel-Crafts acylation reaction temperature is -5-30°C; Step 5) In a preferred embodiment, the intermediate d is subjected to a hydrolysis reaction to obtain a compound, by In the hydrolysis reaction, a hydroxyl group or an alkoxy group can be introduced into the intermediate d. Preferably, the reaction temperature of the hydrolysis reaction is 20-100° C., and limiting the temperature of the hydrolysis reaction within the above range is beneficial to increase the hydrolysis efficiency, thereby increasing the yield of the photoinitiator. Preferably, before the hydrolysis reaction, the above preparation method further includes adding a first organic solvent, an inorganic base and a phase transfer catalyst to the reaction system. The addition of the first organic solvent is beneficial to improve the compatibility between the reaction raw materials, and the addition of the inorganic base and the phase transfer catalyst is beneficial to increase the reaction rate of the reaction and the yield of the photoinitiator. More preferably, the inorganic base is KOH and/or NaOH. More preferably, the phase transfer catalyst is a quaternary ammonium salt phase transfer catalyst. Further preferably, the phase transfer catalyst includes but not limited to tetrabutylammonium bromide, tetrapropylammonium bromide, tetra-n-butylammonium, trichloride One or more of the group consisting of ethylbenzylammonium and tetrabutylammonium hydrogen sulfate.
上述制备方法中，对使用的溶剂种类并没有特别限定，只要能够溶解原料且对反应无不良影响即可，因而第一有机溶剂可以选用本领域常用的溶剂。优选地，第一有机溶剂包括但不限于二氯甲烷、二氯乙烷、苯、二甲苯和乙腈组成的组中的一种或多种。In the above preparation method, the type of solvent used is not particularly limited, as long as it can dissolve the raw materials and has no adverse effect on the reaction. Therefore, the first organic solvent can be a solvent commonly used in the art. Preferably, the first organic solvent includes but is not limited to one or more of the group consisting of dichloromethane, dichloroethane, benzene, xylene and acetonitrile.
在另一种优选的实施方式中，中间体d与含非羟基光活性基团的化合物进行取代脱卤反应，得到光引发剂。In another preferred embodiment, the intermediate d undergoes substitution dehalogenation reaction with a compound containing a non-hydroxyl photoactive group to obtain a photoinitiator.
为了进一步提高脱卤反应中卤原子的脱除率，优选地，脱卤反应的反应温度为40～160℃。In order to further increase the removal rate of halogen atoms in the dehalogenation reaction, preferably, the reaction temperature of the dehalogenation reaction is 40-160°C.
为了提高各反应原料之间的相溶性，上述脱卤反应可以在第二有机溶剂的存在下进行。优选地，第二有机溶剂包括但不限于二氯甲烷、二氯乙烷、苯、二甲苯和乙腈组成的组中的一种或多种；In order to improve the compatibility between the reaction raw materials, the above-mentioned dehalogenation reaction may be carried out in the presence of a second organic solvent. Preferably, the second organic solvent includes but is not limited to one or more of the group consisting of dichloromethane, dichloroethane, benzene, xylene and acetonitrile;
优选地，含非羟基光活性基团的化合物包括但不限于N,N-二甲基、N,N-二乙基、吗啉、硫代吗啉和哌啶组成的组中的一种或多种。相比于其它现有的含非羟基光活性基团的化合物，采用上述含非羟基光活性基团的化合物有利于进一步提高光引发剂的引发效率和感度。Preferably, the compound containing a non-hydroxyl photoactive group includes, but is not limited to, one or the group consisting of N,N-dimethyl, N,N-diethyl, morpholine, thiomorpholine and piperidine. Many kinds. Compared with other existing non-hydroxyl photoactive group-containing compounds, the use of the above-mentioned non-hydroxyl photoactive group-containing compound is beneficial to further improve the initiation efficiency and sensitivity of the photoinitiator.
下面将结合实施例进一步说明本发明的有益效果。Hereinafter, the beneficial effects of the present invention will be further described in conjunction with the embodiments.
实施例1Example 1
Figure PCTCN2020135471-appb-000017
Figure PCTCN2020135471-appb-000017
13,13-双(4-(2-羟基-2-甲基丙醇基)苄基)-6H-茚并[1,2-b]蒽-6,11(13H)-二酮的制备。Preparation of 13,13-bis(4-(2-hydroxy-2-methylpropanol)benzyl)-6H-indeno[1,2-b]anthracene-6,11(13H)-dione.
步骤(1)：2-(9H-芴-2-羰基)苯甲酸的制备Step (1): Preparation of 2-(9H-fluorene-2-carbonyl)benzoic acid
Figure PCTCN2020135471-appb-000018
Figure PCTCN2020135471-appb-000018
向500mL的四口烧瓶中加入二氯甲烷400克、芴50克和邻苯二甲酸酐44.1克，搅拌，冰水浴冷却，温度降至0℃，开始批加三氯化铝44克，批加过程体系温度控制在10℃以下，同时用稀碱液作吸收尾气，三氯化铝约20分钟加完，体系继续常温搅拌1小时，停止反应。将反应液缓慢倒入冰水400克中，固体析出，减压过滤，滤饼用甲醇打浆2小时，过滤，得到类白色粉末状固体湿品，湿品放入50℃烘箱中烘干5小时，得类白色固体粉末65克，收率91.2％，纯度99.1％。Add 400 grams of dichloromethane, 50 grams of fluorene and 44.1 grams of phthalic anhydride to a 500mL four-necked flask, stir, cool in an ice-water bath, and drop the temperature to 0°C. Start adding 44 grams of aluminum trichloride in batches. The temperature of the process system is controlled below 10°C, and the dilute lye is used as the tail gas for absorption. The aluminum trichloride is added in about 20 minutes. The system continues to stir at room temperature for 1 hour to stop the reaction. The reaction solution was slowly poured into 400 grams of ice water, the solids separated out, filtered under reduced pressure, the filter cake was slurried with methanol for 2 hours, filtered to obtain an off-white powdery solid wet product, and the wet product was dried in an oven at 50°C for 5 hours , To obtain 65 grams of off-white solid powder, with a yield of 91.2% and a purity of 99.1%.
步骤(2)：6H-茚并[1,2-b]蒽-6,11(13H)-二酮的制备Step (2): Preparation of 6H-indeno[1,2-b]anthracene-6,11(13H)-dione
Figure PCTCN2020135471-appb-000019
Figure PCTCN2020135471-appb-000019
在250mL四口烧瓶中加入多聚磷酸270克、2-(9H-芴-2-羰基)苯甲酸27克，100℃油浴加热反应，体系保温反应4小时，停止反应。待体系温度降至室温，将反应液缓慢倒入冰水中，搅拌，黄色固体析出，减压过滤，滤饼水洗3次至中性，滤饼用甲醇打浆1小时，减压过滤，得到黄色固体湿品，湿品放入50℃烘箱烘干5小时，得到黄色固体粉末40克，收率88.8％，纯度98.8％。步骤(2)产物结构通过核磁共振氢谱得到确认，具体表征结果如下： 1H-NMR(CDCl 3，500MHz):δ8.60(s,1H)8.30-8.09(m,4H),7.90-7.87(m,2H),7.55-7.52(m,1H),7.50-7.40(m,2H),4.24(s,2H)。 270 grams of polyphosphoric acid and 27 grams of 2-(9H-fluorene-2-carbonyl)benzoic acid were added to a 250mL four-necked flask. The reaction was heated in an oil bath at 100°C, and the system was kept for 4 hours to stop the reaction. After the temperature of the system dropped to room temperature, the reaction solution was slowly poured into ice water, stirred, yellow solid precipitated out, filtered under reduced pressure, the filter cake was washed 3 times with water until it became neutral, the filter cake was slurried with methanol for 1 hour, and filtered under reduced pressure to obtain a yellow solid The wet product is placed in an oven at 50°C for drying for 5 hours to obtain 40 grams of yellow solid powder with a yield of 88.8% and a purity of 98.8%. Step (2) The product structure was confirmed by proton nuclear magnetic resonance spectroscopy. The specific characterization results are as follows: 1 H-NMR (CDCl 3 , 500MHz): δ8.60(s,1H)8.30-8.09(m,4H),7.90-7.87 (m, 2H), 7.55-7.52 (m, 1H), 7.50-7.40 (m, 2H), 4.24 (s, 2H).
步骤(3)：13,13-二苄基-6H-茚并[1,2-b]蒽-6,11(13H)-二酮Step (3): 13,13-dibenzyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione
Figure PCTCN2020135471-appb-000020
Figure PCTCN2020135471-appb-000020
向1L的四口烧瓶中加入二氯甲烷400g、6H-茚并[1,2-b]蒽-6,11(13H)-二酮50g、氯化苄64g和四丁基溴化铵1g，搅拌，氮气保护，水浴30℃下滴加50％氢氧化钠溶液120g，控制体系温度在35℃以下，15min加完，加完体系升温至回流反应8h，取样检测原料反应完全，停止反应，降至室温。向反应液中加入水100g，分出有机层，有机层用水洗3次至中性，有机相蒸干溶剂，加入甲醇200g析晶，搅拌析晶1h，过滤，湿品烘干，得到黄色固体73.4g，收率91.3％，纯度98.2％。MS(m/z):477(M+1) +。 Add 400 g of dichloromethane, 50 g of 6H-indeno[1,2-b]anthracene-6,11(13H)-dione, 64 g of benzyl chloride and 1 g of tetrabutylammonium bromide into a 1L four-necked flask, Stir, under nitrogen protection, add 120g of 50% sodium hydroxide solution dropwise at 30°C in a water bath, control the temperature of the system below 35°C, add 15min, after adding the system, heat up the system to reflux for 8h, take a sample to check that the raw material has reacted completely, stop the reaction, and drop To room temperature. Add 100g of water to the reaction solution, separate the organic layer, wash the organic layer 3 times with water until it is neutral, evaporate the organic phase to dry the solvent, add 200g of methanol to crystallize, stir and crystallize for 1h, filter, dry the wet product to obtain a yellow solid 73.4g, yield 91.3%, purity 98.2%. MS(m/z): 477(M+1) + .
步骤(4)：13,13-双(4-(2-氯-2-甲基丙醇基)苄基)-6H-茚并[1,2-b]蒽-6,11(13H)-二酮Step (4): 13,13-bis(4-(2-chloro-2-methylpropanol)benzyl)-6H-indeno[1,2-b]anthracene-6,11(13H)- Diketone
Figure PCTCN2020135471-appb-000021
Figure PCTCN2020135471-appb-000021
在500mL四口烧瓶中加入二氯甲烷300克、13,13-二苄基-6H-茚并[1,2-b]蒽-6,11(13H)-二酮30克、氯代异丁酰氯19.6克，体系在冰水浴下搅拌，待体系温度降至0℃时，分批加入三氯化铝20.12克，批加过程控制体系温度在10℃以下，同时用稀碱液作尾气吸收，10分钟加完三氯化铝，体系保温反应1小时。停止反应，将反应液缓慢倒入冰水300克中，分出有机层，有机层用水600克洗2次，将有机层倒入500mL四口烧瓶中，蒸出有机溶剂，加入甲醇60克在-10℃下搅拌析晶2小时，过滤，滤饼用甲醇少许漂洗，得到浅黄色固体湿品，湿品放入50℃烘箱避光烘干5小时，得到黄色固体粉末39.8克，收率92.1％，纯度98.3％。In a 500mL four-necked flask, add 300 grams of dichloromethane, 30 grams of 13,13-dibenzyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione, and chloroisobutyl 19.6 g of acid chloride, and the system is stirred in an ice water bath. When the temperature of the system drops to 0°C, 20.12 g of aluminum trichloride is added in batches. The batch addition process controls the temperature of the system below 10°C and uses dilute lye as tail gas absorption. The aluminum trichloride was added in 10 minutes, and the system was kept warm and reacted for 1 hour. Stop the reaction, slowly pour the reaction solution into 300 grams of ice water, separate the organic layer, wash the organic layer twice with 600 grams of water, pour the organic layer into a 500 mL four-necked flask, distill the organic solvent, add 60 grams of methanol in Stir and crystallize at -10°C for 2 hours, filter, and rinse the filter cake with methanol a little to obtain a light yellow solid wet product. The wet product is placed in an oven at 50°C and protected from light for 5 hours to obtain 39.8 grams of yellow solid powder. The yield is 92.1. %, the purity is 98.3%.
步骤(5)产品13,13-双(4-(2-羟基-2-甲基丙醇基)苄基)-6H-茚并[1,2-b]蒽-6,11(13H)-二酮的制备Step (5) product 13,13-bis(4-(2-hydroxy-2-methylpropanol)benzyl)-6H-indeno[1,2-b]anthracene-6,11(13H)- Preparation of diketone
Figure PCTCN2020135471-appb-000022
Figure PCTCN2020135471-appb-000022
向250mL四口烧瓶中加入甲苯60克，13,13-双(4-(2-氯-2-甲基丙醇基)苄基)-6H-茚并[1,2-b]蒽-6,11(13H)-二酮30克，四丁基溴化铵1克，搅拌，滴加25％氢氧化钠溶液60克，控制体系温度在30℃以下，10分钟加完，体系在80℃水浴下加热反应1小时，停止反应。待体系温度降至室温，分出有机层，有机层用水200克洗至中性，有机层倒入250mL四口烧瓶中，加入活性炭1克，搅拌1小时，过滤，滤饼用甲苯少许漂洗，合并有机相，滤液倒入250mL四口烧瓶中，蒸出有机溶剂，加入正己烷50克搅拌析晶1小时，过滤，滤饼用正己烷少许漂洗，得到白色固体湿品，湿品放入50℃烘箱避光烘干3小时，得到化合物1黄色固体粉末20.5克，收率72.3％，纯度99.1％。Add 60 grams of toluene into a 250mL four-necked flask, 13,13-bis(4-(2-chloro-2-methylpropanol)benzyl)-6H-indeno[1,2-b]anthracene-6 ,11(13H)-dione 30g, tetrabutylammonium bromide 1g, stir, add dropwise 25% sodium hydroxide solution 60g, control the temperature of the system below 30℃, add it in 10 minutes, the system is at 80℃ The reaction was stopped by heating under a water bath for 1 hour. When the temperature of the system drops to room temperature, separate the organic layer, wash the organic layer with 200 grams of water until it is neutral, pour the organic layer into a 250 mL four-neck flask, add 1 gram of activated carbon, stir for 1 hour, filter, and rinse the filter cake with toluene a little. Combine the organic phases, pour the filtrate into a 250mL four-necked flask, distill off the organic solvent, add 50 grams of n-hexane and stir for 1 hour to crystallize, filter, and rinse the filter cake with n-hexane to obtain a white solid wet product. It was dried in an oven at ℃ and protected from light for 3 hours to obtain 20.5 g of compound 1 as a yellow solid powder with a yield of 72.3% and a purity of 99.1%.
步骤(5)所得最终产品结构通过核磁共振氢谱得到确认，具体表征结果如下： 1H-NMR(CDCl 3，500MHz):δ8.37-8.29(m,5H),8.09-7.95(m,2H),7.55-7.29(m,3H),6.93-6.80(m,8H),4.87-4.57(s,2H),3.17(m,4H),1.39(s,12H)。MS(m/z):649(M+1) +。 The structure of the final product obtained in step (5) was confirmed by proton nuclear magnetic resonance spectroscopy. The specific characterization results are as follows: 1 H-NMR (CDCl 3 , 500MHz): δ8.37-8.29(m,5H), 8.09-7.95(m,2H) ), 7.55-7.29 (m, 3H), 6.93-6.80 (m, 8H), 4.87-4.57 (s, 2H), 3.17 (m, 4H), 1.39 (s, 12H). MS (m/z): 649 (M+1) + .
实施例2Example 2
Figure PCTCN2020135471-appb-000023
Figure PCTCN2020135471-appb-000023
13,13-双(4-(2-吗啉基-2-甲基丙醇基)苄基)-6H-茚并[1,2-b]蒽-6,11(13H)-二酮的制备。13,13-Bis(4-(2-morpholinyl-2-methylpropanol)benzyl)-6H-indeno[1,2-b]anthracene-6,11(13H)-dione preparation.
向500mL四口烧瓶中加入13,13-双(4-(2-氯-2-甲基丙醇基)苄基)-6H-茚并[1,2-b]蒽-6,11(13H)-二酮50g、吗啉200g，100℃加热回流6h，液相检测反应完全，将反应液倒入水中搅拌，黄色固体析出，抽滤，水洗，甲醇重结晶得化合物2黄色固体50g，收率87.0％，纯度98.57％。Add 13,13-bis(4-(2-chloro-2-methylpropanol)benzyl)-6H-indeno[1,2-b]anthracene-6,11(13H )-Diketone 50g, morpholine 200g, heated to reflux at 100°C for 6h, liquid phase detection reaction is complete, the reaction liquid is poured into water and stirred, a yellow solid precipitates, suction filtration, water washing, methanol recrystallization to obtain compound 2 yellow solid 50g, The rate is 87.0%, and the purity is 98.57%.
产物结构通过核磁共振氢谱和质谱得到确认，具体表征结果如下： 1H-NMR(CDCl 3，500MHz):δ8.39-8.28(m,5H),8.01-7.94(m,2H),7.54-7.28(m,3H),6.90-6.80(m,8H),3.66-3.50(t,8H),3.15(m,4H),2.49-2.39(t,8H),1.40(s,12H)。MS(m/z):787(M+1) +。 The structure of the product was confirmed by proton nuclear magnetic resonance spectroscopy and mass spectrometry. The specific characterization results are as follows: 1 H-NMR (CDCl 3 , 500MHz): δ8.39-8.28(m,5H),8.01-7.94(m,2H),7.54- 7.28 (m, 3H), 6.90-6.80 (m, 8H), 3.66-3.50 (t, 8H), 3.15 (m, 4H), 2.49-2.39 (t, 8H), 1.40 (s, 12H). MS (m/z): 787 (M+1) + .
参照上述方法，通过不同的原料、原料配比和反应条件，可得到不同结构的化合物。例如，如表1所示。With reference to the above method, through different raw materials, raw material ratios and reaction conditions, compounds with different structures can be obtained. For example, as shown in Table 1.
表1Table 1
Figure PCTCN2020135471-appb-000024
Figure PCTCN2020135471-appb-000024
Figure PCTCN2020135471-appb-000025
Figure PCTCN2020135471-appb-000025
性能评价Performance evaluation
1、固化性1. Curability
将固化组合物在黄光灯下搅拌，然后取料在PET模板上利用滚涂成膜，在80℃下干燥3min，得到干膜厚度为2μm的涂膜。然后将上述涂膜冷却至室温，用UV-LED(385nm)灯(曝光机型号：RW-UV70201，单次曝光量50mJ/cm 2)照射，以对上述涂膜进行曝光，使其固化成膜。以涂膜固化成固化膜达到表干所经过履式曝光带的次数评价，经过次数越多，表明固化速度越不理想。 The cured composition was stirred under a yellow light, and then the material was taken and rolled onto a PET template to form a film, and dried at 80° C. for 3 minutes to obtain a coating film with a dry film thickness of 2 μm. Then cool the above-mentioned coating film to room temperature, and irradiate it with a UV-LED (385nm) lamp (exposure machine model: RW-UV70201, single exposure 50mJ/cm 2 ) to expose the above-mentioned coating film and make it solidify into membrane. It is evaluated by the number of times of the crawler exposure belt that the coating film is cured into a cured film to reach surface dryness.
2、迁移性2. Migration
用乙醇作溶剂，将光引发剂实施例及对比例分别配成1×10 -5mol/L的溶液，通过UV3010紫外分光光度计测定其最大吸收波长及其吸光度A1，并通过公式(1)计算出摩尔消光系数： Using ethanol as the solvent, the photoinitiator examples and comparative examples were prepared into 1×10 -5 mol/L solutions, and the maximum absorption wavelength and absorbance A1 were measured by UV3010 ultraviolet spectrophotometer, and the formula (1) Calculate the molar extinction coefficient:
c＝A/ε×b      (1)c=A/ε×b (1)
R＝100×c/c 1      (2) R=100×c/c 1 (2)
称取0.05g上述光固化组合物高压汞灯下制得的固化膜，分别放入30g乙醇中浸泡，常温放置24h后取相同体积的浸泡液用紫外分光光度计测量其最大吸收波长处的吸光度A2。通过公式(1)计算出各个固化膜中迁移出来的光引发剂的浓度，并以光引发剂TPO的浓度值作为参照基准，通过公式(2)测算出各种光引发剂的相对迁移率。Weigh out 0.05g of the cured film prepared under the high-pressure mercury lamp of the above-mentioned photocurable composition, and soak them in 30g of ethanol. After 24h at room temperature, take the same volume of soaking solution and measure the absorbance at the maximum absorption wavelength with an ultraviolet spectrophotometer. A2. The concentration of the photoinitiator migrated from each cured film is calculated by formula (1), and the concentration of the photoinitiator TPO is used as a reference, and the relative mobility of various photoinitiators is calculated by formula (2).
上述公式中，c为相对浓度(mol/L)，c1为TPO的相对浓度，A为吸光度，ε为摩尔吸光系数(L/mol·cm)；b为样品池厚度(cm)；R相对迁移率。In the above formula, c is the relative concentration (mol/L), c1 is the relative concentration of TPO, A is the absorbance, ε is the molar absorption coefficient (L/mol·cm); b is the thickness of the sample cell (cm); R is the relative migration rate.
3、气味性3. Odor
固化组合物的气味性通过鼻子闻来评判，测试结果分为1(无气味)、2(有气味)、3(刺激性气味)三个等级。The odor of the cured composition is judged by sniffing, and the test results are divided into three levels: 1 (no odor), 2 (odor), and 3 (irritant odor).
具体数据见表2。See Table 2 for specific data.
表2Table 2
Figure PCTCN2020135471-appb-000026
Figure PCTCN2020135471-appb-000026
Figure PCTCN2020135471-appb-000027
Figure PCTCN2020135471-appb-000027
从上述配方测试结果可以看出，本发明的通式(I)所示的光引发剂单独使用，就能较好的固化，且不发生迁移，具有低气味特性，综合性能明显优于现有的光引发剂产品，具有广阔的市场前景。It can be seen from the above formula test results that the photoinitiator represented by the general formula (I) of the present invention can be cured better without migration, has low odor characteristics, and the overall performance is significantly better than existing ones. The photoinitiator products have broad market prospects.
实施例7Example 7
1、光固化油墨的配制1. Preparation of light-curable ink
下面示例性地以本领域最常用的烯属不饱和聚合单体、烯属不饱和聚合低聚物、引发剂、着色剂以及其他组分为例进行说明，各相应组分也可以替换成以上说明书中其它化合物。按照表3至6中所示配方，分别配制实施例7-31、对比例3-6的光固化油墨，另外如无特别说明，各实施例中所述数量均为重量份数。The following exemplarily takes the most commonly used ethylenically unsaturated polymerized monomers, ethylenically unsaturated polymerized oligomers, initiators, colorants and other components in the field as examples for description, and each corresponding component can also be replaced with the above Other compounds in the specification. According to the formulas shown in Tables 3 to 6, the photocurable inks of Examples 7-31 and Comparative Examples 3-6 were respectively prepared. In addition, unless otherwise specified, the quantities in each example are parts by weight.
表3(标签印刷柔印油墨)Table 3 (flexo ink for label printing)
Figure PCTCN2020135471-appb-000028
Figure PCTCN2020135471-appb-000028
表4(UV柔印油墨)Table 4 (UV flexo printing ink)
Figure PCTCN2020135471-appb-000029
Figure PCTCN2020135471-appb-000029
Figure PCTCN2020135471-appb-000030
Figure PCTCN2020135471-appb-000030
表5(丝印纸张上油墨)Table 5 (Ink on silk screen paper)
Figure PCTCN2020135471-appb-000031
Figure PCTCN2020135471-appb-000031
Figure PCTCN2020135471-appb-000032
Figure PCTCN2020135471-appb-000032
表6 UV胶印油墨Table 6 UV offset printing ink
Figure PCTCN2020135471-appb-000033
Figure PCTCN2020135471-appb-000033
表7Table 7
Figure PCTCN2020135471-appb-000034
Figure PCTCN2020135471-appb-000034
表3至7中，各组分中商品名的含义如下：In Tables 3 to 7, the meanings of the trade names in each component are as follows:
环氧丙烯酸酯AgiSyn 3050、三丙二醇二丙烯酸酯AgiSyn 2815、丙氧化甘油三丙烯酸酯AgiSyn 2837、芳香族聚氨酯丙烯酸酯NeoRad U-6288、乙氧化三羟甲基丙烷三丙烯酸酯AgiSyn 2836、羟甲基丙烷三丙烯酸酯AgiSyn 2811、1，6-二羟基乙烷丙烯酸酯AgiSyn 2816来源于帝斯曼；Epoxy acrylate AgiSyn 3050, tripropylene glycol diacrylate AgiSyn 2815, propylene oxide glycerol triacrylate AgiSyn 2837, aromatic urethane acrylate NeoRad U-6288, ethoxylated trimethylolpropane triacrylate AgiSyn 2836, methylol Propane triacrylate AgiSyn 2811, 1,6-dihydroxyethane acrylate AgiSyn 2816 comes from DSM;
聚酯丙烯酸酯CN2271、环氧化大豆油丙烯酸酯CN111、聚酯丙烯酸酯CN2200、环氧丙烯酸酯CN2204、聚氨酯酯丙烯酸酯CN9013来源沙多玛；Polyester acrylate CN2271, epoxidized soybean oil acrylate CN111, polyester acrylate CN2200, epoxy acrylate CN2204, urethane acrylate CN9013 are from Sartomer;
对甲氧基苯酚、甲基对苯二酚来源于来源于上海诺泰化工；The p-methoxyphenol and methylhydroquinone are from Shanghai Nuotai Chemical;
聚醚改性聚二甲基硅氧烷BYK-371来源于毕克化学；The polyether modified polydimethylsiloxane BYK-371 comes from BYK Chemicals;
其他着色剂来源于山东宏润化工；Other colorants come from Shandong Hongrun Chemical Industry;
聚乙烯蜡型号：EVA3来源于巴斯夫；Polyethylene wax model: EVA3 comes from BASF;
2、性能测试和评价2. Performance test and evaluation
1、固化性1. Curability
将固化组合物在黄光灯下搅拌，然后取料在PET模板上利用滚涂成膜，在80℃下干燥3min，得到干膜厚度为2μm的涂膜。然后将上述涂膜冷却至室温，用UV-LED灯照射，以对上述涂膜进行曝光，使其固化成膜。以涂膜固化成固化膜达到表干所经过履式曝光带的次数评价，经过次数越多，表明固化速度越不理想。The cured composition was stirred under a yellow light, and then the material was taken and rolled onto a PET template to form a film, and dried at 80° C. for 3 minutes to obtain a coating film with a dry film thickness of 2 μm. Then, the coating film is cooled to room temperature and irradiated with a UV-LED lamp to expose the coating film to be cured into a film. The coating film is cured into a cured film to reach surface dryness through the evaluation of the number of crawler exposure belts, the more the number of passes, the less ideal the curing speed.
2、迁移性2. Migration
将光固化组合物按上述光固化条件完全固化，将样品制成同样大小50*50mm的膜，将50*50mm的膜剪成4份浸于50mL95％的乙醇中，50℃，浸泡2h，取浸泡液进行高效液相色谱(HPLC)分析。对每种引发剂进行标准曲线的测定，根据该引发剂在高效液相色谱(HPLC)中的出峰面积，计算出其对应的浓度，单位为g/mLThe light-curing composition is completely cured under the above-mentioned light-curing conditions, the sample is made into a film of the same size of 50*50mm, and the 50*50mm film is cut into 4 parts soaked in 50mL of 95% ethanol, 50℃, soaked for 2h, and taken The soaking liquid was analyzed by high performance liquid chromatography (HPLC). Measure the standard curve of each initiator, and calculate the corresponding concentration according to the peak area of the initiator in high performance liquid chromatography (HPLC), the unit is g/mL
3、气味性3. Odor
固化组合物的气味性通过鼻子闻来评判，测试结果分为1(无气味)、2(有气味)、3(刺激性气味)三个等级The odor of the cured composition is judged by the nose, and the test results are divided into three levels: 1 (no odor), 2 (odor), and 3 (irritating odor)
4、附着牢度检测4. Adhesion fastness detection
按照GB/T 13217.7-2009液体油墨附着牢度检验方法进行，具体实施方法如下：在温度25±1℃、湿度65％±5％条件下，将胶带粘贴在油墨印刷面，在胶带压滚机上往返滚压3次。放置5min，将试样夹在A盘上，露头的胶带固定在B盘上(符合标准GB/T 7707-2008图1的)。然后开机，A盘以速度0.6m/s～1.0m/s旋转揭开胶带，用宽20nm的半透明毫米格纸覆盖在被揭部分。分别数出油墨层所占的格数和被揭去的油墨层所占的格数，按下式计算：According to the GB/T 13217.7-2009 liquid ink adhesion fastness test method, the specific implementation method is as follows: at a temperature of 25±1℃ and a humidity of 65%±5%, stick the tape on the printing surface of the ink and place it on the tape roller Roll back and forth 3 times. Place it for 5 minutes, clamp the sample on the A plate, and fix the exposed tape on the B plate (in accordance with the standard GB/T 7707-2008 in Figure 1). Then turn it on, and drive A at a speed of 0.6m/s～1.0m/s to uncover the tape, and cover the uncovered part with a translucent millimeter grid paper with a width of 20nm. Count the number of grids occupied by the ink layer and the number of grids occupied by the removed ink layer respectively, and calculate as follows:
A(％)＝A1/(A1+A2)*100％A(%)=A1/(A1+A2)*100%
式中：A——油墨附着牢度；In the formula: A-ink adhesion fastness;
A1——油墨层的格数；A1——The number of grids of the ink layer;
A2——被揭去的油墨层的格数；A2——The number of cells of the ink layer removed;
其中≥90％为符合性能指标。Among them, ≥90% meets the performance index.
评价结果汇总于表8和9。The evaluation results are summarized in Tables 8 and 9.
表8Table 8
Figure PCTCN2020135471-appb-000035
Figure PCTCN2020135471-appb-000035
Figure PCTCN2020135471-appb-000036
Figure PCTCN2020135471-appb-000036
表9Table 9
Figure PCTCN2020135471-appb-000037
Figure PCTCN2020135471-appb-000037
表9中实施例33的附着力虽然≥90，但是比其它实施例的附着力差一些。Although the adhesion force of Example 33 in Table 9 is ≥90, it is slightly worse than the adhesion force of other examples.
从表8和9测试结果看，与采用市面上常见光引发剂进行对比，本发明的光固化组合物应用于不同油墨配方中，均具有固化速度快，不发生迁移、低气味的特点。弥补了现有引发剂存在的不足，具有很好的应用前景。From the test results of Tables 8 and 9, compared with using common photoinitiators on the market, the photocurable composition of the present invention is applied to different ink formulations and has the characteristics of fast curing speed, no migration, and low odor. It makes up for the shortcomings of the existing initiators and has good application prospects.
综上所述，本发明式(I)所示化合物作为光引发剂在应用在光固化领域，能够表现出优异的综合应用性能，具有广阔的应用前景。In summary, the compound represented by formula (I) of the present invention is used as a photoinitiator in the field of light curing, can exhibit excellent comprehensive application performance, and has broad application prospects.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above are only preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

  1. 一种光引发剂，其特征在于，所述光引发剂具有式(I)所示的结构：A photoinitiator, characterized in that the photoinitiator has a structure represented by formula (I):
    Figure PCTCN2020135471-appb-100001
    Figure PCTCN2020135471-appb-100001
    其中，R 1和R 2各自独立地选自C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 6～C 20的芳基取代的C 1～C 12的烷基和C 1～C 12的烷基取代的C 3～C 8的环烷基中的任意一种，R 1和R 2可彼此相连成环；R 3为光活性基团；两个Ar各自独立地选自取代或未被取代的亚芳基或取代或未被取代的亚杂芳基中的任意一种； Wherein, R 1 and R 2 are each independently selected from C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 cycloalkyl, C 3 ～C 8 Cycloalkyl substituted C 1 to C 12 alkyl, C 6 to C 20 aryl substituted C 1 to C 12 alkyl, and C 1 to C 12 alkyl substituted C 3 to C 8 ring Any of the alkyl groups, R 1 and R 2 can be connected to each other to form a ring; R 3 is a photoactive group; each of the two Ar is independently selected from substituted or unsubstituted arylene or substituted or unsubstituted Any one of the heteroarylene groups;
    R a1、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基、-OR d1、-COR d1、-COOR d1、-SR d1、-SO 2R d1和-CONR d1R d2中的任意一种，其中R d1和R d2各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基和C 2～C 20的杂环基中的任意一种； R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are each independently selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 Branched chain alkyl group, C 3 ～C 20 cycloalkyl group, C 3 ～C 8 cycloalkyl group substituted C 1 ～C 12 alkyl group, C 1 ～C 12 alkyl group substituted C 3 ～C 8 Cycloalkyl group, C 7 ～C 20 aralkyl group, C 2 ～C 20 heterocyclic group, -OR d1 , -COR d1 , -COOR d1 , -SR d1 , -SO 2 R d1 and -CONR d1 Any one of R d2 , wherein R d1 and R d2 are each independently selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 ring Alkyl groups, C 1 ～C 12 alkyl groups substituted with C 3 ～C 8 cycloalkyl groups, C 3 ～C 8 cycloalkyl groups substituted with C 1 ～C 12 alkyl groups, C 7 ～C 20 aryl groups Any one of an alkyl group and a C 2 ～C 20 heterocyclic group;
    R a2选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基、-NO 2、-OR e1、-COR e1、-COOR e1、-SR e1、-SO 2R e1和-CONR e1R e2中的任意一种，其中R e1和R e2各自独立地选自氢、C 1～C 20的直链烷基、C 1～C 20的支链烷基、C 3～C 20的环烷基、C 3～C 8的环烷基取代的C 1～C 12的烷基、C 1～C 12的烷基取代的C 3～C 8的环烷基、C 7～C 20的芳烷基、C 2～C 20的杂环基和-C(R 1)(R 2)(R 3)中的任意一种。 R a2 is selected from hydrogen, C 1 ～C 20 linear alkyl, C 1 ～C 20 branched alkyl, C 3 ～C 20 cycloalkyl, C 3 ～C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, -NO 2. Any one of -OR e1 , -COR e1 , -COOR e1 , -SR e1 , -SO 2 R e1 and -CONR e1 R e2 , wherein R e1 and R e2 are each independently selected from hydrogen, C 1 ~C 20 linear alkyl, C 1 to C 20 branched alkyl, C 3 to C 20 cycloalkyl, C 3 to C 8 cycloalkyl substituted C 1 to C 12 alkyl, C 1 to C 12 alkyl substituted C 3 to C 8 cycloalkyl, C 7 to C 20 aralkyl, C 2 to C 20 heterocyclic group, and -C(R 1 )(R 2 ) Any one of (R 3 ).
  2. 根据权利要求1所述的光引发剂，其特征在于，所述R 3选自羟基、烷氧基、N，N-二烷基、N-吗啉基、N-硫代吗啉基或N-取代哌嗪基中的任意一种。 The photoinitiator according to claim 1, wherein the R 3 is selected from hydroxyl, alkoxy, N,N-dialkyl, N-morpholinyl, N-thiomorpholinyl or N -Any one of the substituted piperazinyl groups.
  3. 根据权利要求1所述的光引发剂，其特征在于，所述R 1和所述R 2各自独立地选自C 1～C 4的直链烷基、C 1～C 4的支链烷基、C 3～C 5的环烷基取代的C 1～C 3的烷基、C 6～C 12的芳基取代的C 1～C 3的烷基中的任意一种，或者所述R 1和所述R 2彼此相连形成C 3～C 6的环烷基。 The photoinitiator of claim 1, wherein the R 1 and the R 2 are each independently selected from C 1 ～C 4 linear alkyl groups, C 1 ～C 4 branched chain alkyl groups , C 3 to C 5 cycloalkyl substituted C 1 to C 3 alkyl group, C 6 to C 12 aryl substituted C 1 to C 3 alkyl group, or any one of the R 1 And the R 2 are connected to each other to form a C 3 -C 6 cycloalkyl group.
  4. 根据权利要求1所述的光引发剂，其特征在于，所述Ar选自取代或未取代的亚苯基、取代或未取代的亚吡啶基、取代或未取代的亚噻吩基和取代或未取代的亚呋喃基中的任意一种。The photoinitiator according to claim 1, wherein the Ar is selected from substituted or unsubstituted phenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted thienylene, and substituted or unsubstituted phenylene Any of the substituted furanylene groups.
  5. 根据权利要求1至4中任一项所述的光引发剂，其特征在于，所述R a2选自氢、C 1～C 10的直链烷基、C 1～C 10的支链烷基、C 7～C 10的芳烷基、C 2～C 10的杂环基、-NO 2、-OR e1、-COR e1、-COOR e1或-CONR e1R e2，其中R e1和R e2各自独立地表示氢、C 1～C 10的直链烷基、C 1～C 10的支链烷基、C 3～C 10的环烷基、C 3～C 8的环烷基取代的C 1～C 5的烷基、C 1～C 5的烷基取代的C 3～C 8的环烷基、C 7～C 10的芳烷基、C 2～C 20的杂环基和-C(R 1)(R 2)(R 3)中的任意一种； The photoinitiator according to any one of claims 1 to 4, wherein the R a2 is selected from hydrogen, C 1 ～C 10 linear alkyl group, C 1 ～C 10 branched chain alkyl group , C 7 ～C 10 aralkyl group, C 2 ～C 10 heterocyclic group, -NO 2 , -OR e1 , -COR e1 , -COOR e1 or -CONR e1 R e2 , where R e1 and R e2 are each It independently represents hydrogen, C 1 ～C 10 linear alkyl, C 1 ～C 10 branched alkyl, C 3 ～C 10 cycloalkyl, C 3 ～C 8 cycloalkyl substituted C 1 ～C 5 alkyl, C 1 ～C 5 alkyl substituted C 3 ～C 8 cycloalkyl, C 7 ～C 10 aralkyl, C 2 ～C 20 heterocyclic group and -C( Any one of R 1 )(R 2 )(R 3 );
    优选的，所述R 1和所述R 2各自独立地选自C 1～C 4的直链烷基、C 1～C 4的支链烷基、苯基取代的C 1～C 3的烷基中的任意一种，所述R 3选自羟基、烷氧基、N，N-二烷基、N-吗啉基、N-硫代吗啉基中的任意一种，所述R a1、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4为氢，所述R a2选自氢、C 1～C 10的直链烷基、C 1～C 10的支链烷基和-COR e1中的任意一种，R e1为C 1～C 10的直链或支链烷基、C 7～C 10的芳烷基、C 2～C 20的杂芳基和-C(R 1)(R 2)(R 3)中的任意一种； Preferably, said R 1 and said R 2 are each independently selected from C 1 ～C 4 linear alkyl, C 1 ～C 4 branched alkyl, phenyl substituted C 1 ～C 3 alkane Any one of the group, said R 3 is selected from any one of hydroxyl, alkoxy, N,N-dialkyl, N-morpholinyl, N-thiomorpholinyl, said R a1 , R a3 , R a4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are hydrogen, and the R a2 is selected from hydrogen, C 1 ～C 10 linear alkyl group, C 1 ～C Any one of the branched alkyl group of 10 and -COR e1 , R e1 is a straight or branched C 1 ～C 10 alkyl group, a C 7 ～C 10 aralkyl group, or a C 2 ～C 20 hetero Any one of aryl and -C(R 1 )(R 2 )(R 3 );
    优选的，所述R 1和所述R 2彼此相连形成C 3～C 6的环烷基，所述R 3为羟基或烷氧基，所述R a1、R a2、R a3、R a4、R b1、R b2、R c1、R c2、R c3、R c4为氢。 Preferably, the R 1 and the R 2 are connected to each other to form a C 3 to C 6 cycloalkyl group, the R 3 is a hydroxyl group or an alkoxy group, and the Ra1 , Ra2 , Ra3 , Ra4 , R b1 , R b2 , R c1 , R c2 , R c3 , and R c4 are hydrogen.
  6. 根据权利要求5所述的光引发剂，其特征在于，所述光引发剂具有如下结构：The photoinitiator of claim 5, wherein the photoinitiator has the following structure:
    Figure PCTCN2020135471-appb-100002
    Figure PCTCN2020135471-appb-100002
    Figure PCTCN2020135471-appb-100003
    Figure PCTCN2020135471-appb-100003
    Figure PCTCN2020135471-appb-100004
    Figure PCTCN2020135471-appb-100004
  7. 一种光固化组合物，所述光固化组合物包括光引发剂、聚合单体和/或聚合低聚物，其特征在于，所述光引发剂包括权利要求1至6中任一项所述的引发剂；A photocurable composition, the photocurable composition comprising a photoinitiator, a polymerized monomer and/or a polymerized oligomer, wherein the photoinitiator includes the photoinitiator according to any one of claims 1 to 6 The initiator;
    优选的，所述聚合单体为烯属双键的烯属不饱和聚合单体，所述聚合低聚物为烯属不饱和聚合低聚物。Preferably, the polymerized monomer is an ethylenically unsaturated polymerized monomer with an ethylenic double bond, and the polymerized oligomer is an ethylenically unsaturated polymerized oligomer.
  8. 根据权利要求7所述的光固化组合物，其特征在于，所述烯属双键的烯属不饱和聚合单体为任意一种丙烯酸酯类化合物，且所述丙烯酸酯类化合物的官能团种类小于等于3，优选所述光固化组合物中所述烯属双键的烯属不饱和聚合单体的重量百分含量为10％～85％，更优选为20％～65％。The photocurable composition according to claim 7, wherein the ethylenically unsaturated polymerizable monomer of the ethylenic double bond is any type of acrylate compound, and the type of functional group of the acrylate compound is less than It is equal to 3, preferably the weight percentage of the ethylenically unsaturated polymerized monomer of the ethylenic double bond in the photocurable composition is 10%-85%, more preferably 20%-65%.
  9. 一种光固化油墨，包括光固化组合物，其特征在于，所述光固化组合物选自权利要求7或8所述的光固化组合物中的任意一种。A photocurable ink, comprising a photocurable composition, characterized in that the photocurable composition is selected from any one of the photocurable compositions of claim 7 or 8.
  10. 权利要求1至6中任一项所述的光引发剂在光固化领域中的应用；Application of the photoinitiator of any one of claims 1 to 6 in the field of photocuring;
    优选的，所述光固化领域为UV-LED光源的光固化领域。Preferably, the light curing field is the light curing field of a UV-LED light source.
  11. 一种如权利要求1至6中任一项所述的光引发剂的制备方法，其特征在于，包括以下步骤：A method for preparing a photoinitiator according to any one of claims 1 to 6, characterized in that it comprises the following steps:
    1)原料a和原料b傅克酰基化反应得到中间体a；1) Friedel-Crafts acylation reaction of raw material a and raw material b to obtain intermediate a;
    Figure PCTCN2020135471-appb-100005
    Figure PCTCN2020135471-appb-100005
    2)所述中间体a发生脱水反应得到中间体b；2) The intermediate a undergoes a dehydration reaction to obtain the intermediate b;
    Figure PCTCN2020135471-appb-100006
    Figure PCTCN2020135471-appb-100006
    3)所述中间体b和原料c发生取代反应得到中间体c；3) The intermediate b and the raw material c undergo a substitution reaction to obtain the intermediate c;
    Figure PCTCN2020135471-appb-100007
    Figure PCTCN2020135471-appb-100007
    4)所述中间体c与原料d发生傅克酰基化反应，得到中间体d；4) The Friedel-Crafts acylation reaction between the intermediate c and the raw material d to obtain the intermediate d;
    Figure PCTCN2020135471-appb-100008
    Figure PCTCN2020135471-appb-100008
    5)所述中间体d发生取代反应，得到所述光引发剂5) The intermediate d undergoes a substitution reaction to obtain the photoinitiator
    Figure PCTCN2020135471-appb-100009
    Figure PCTCN2020135471-appb-100009
PCT/CN2020/135471 2019-12-19 2020-12-10 Photoinitiator, preparation method therefor and application thereof, and photocurable composition WO2021121135A1 (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120161615A1 (en) * 2009-06-19 2012-06-28 Doosan Corporation Aminoanthracene derivative and an organic electroluminescent element employing the same
CN103048883A (en) * 2012-12-05 2013-04-17 北京化工大学常州先进材料研究院 Photosensitive composition containing polymerizable photoinitiator
KR20140119672A (en) * 2014-08-25 2014-10-10 애경화학 주식회사 Oxime ester photoinitiators with novel structure and reactive liquid crystal compositions, and photoresist compositions comprising the same
CN104371043A (en) * 2014-11-21 2015-02-25 河南金誉包装科技股份有限公司 Thioxanthone acetylfluorene photoinitiator and preparation method thereof
CN104661997A (en) * 2012-05-03 2015-05-27 韩国化学研究院 Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same
CN107325237A (en) * 2016-04-15 2017-11-07 常州强力电子新材料股份有限公司 A kind of Free radical-Cationic Hybrid photocuring system and its application
CN110590533A (en) * 2018-06-12 2019-12-20 常州强力先端电子材料有限公司 Water-based photoinitiator containing fluorene structure and preparation method and application thereof
CN112010997A (en) * 2019-05-30 2020-12-01 常州强力先端电子材料有限公司 Fluorene photoinitiator, preparation method thereof, photocuring composition containing fluorene photoinitiator and application of fluorene photoinitiator in photocuring field

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120161615A1 (en) * 2009-06-19 2012-06-28 Doosan Corporation Aminoanthracene derivative and an organic electroluminescent element employing the same
CN104661997A (en) * 2012-05-03 2015-05-27 韩国化学研究院 Novel oximester fluorine compound, and photopolymerization initiator and photoresist composition comprising same
CN103048883A (en) * 2012-12-05 2013-04-17 北京化工大学常州先进材料研究院 Photosensitive composition containing polymerizable photoinitiator
KR20140119672A (en) * 2014-08-25 2014-10-10 애경화학 주식회사 Oxime ester photoinitiators with novel structure and reactive liquid crystal compositions, and photoresist compositions comprising the same
CN104371043A (en) * 2014-11-21 2015-02-25 河南金誉包装科技股份有限公司 Thioxanthone acetylfluorene photoinitiator and preparation method thereof
CN107325237A (en) * 2016-04-15 2017-11-07 常州强力电子新材料股份有限公司 A kind of Free radical-Cationic Hybrid photocuring system and its application
CN110590533A (en) * 2018-06-12 2019-12-20 常州强力先端电子材料有限公司 Water-based photoinitiator containing fluorene structure and preparation method and application thereof
CN112010997A (en) * 2019-05-30 2020-12-01 常州强力先端电子材料有限公司 Fluorene photoinitiator, preparation method thereof, photocuring composition containing fluorene photoinitiator and application of fluorene photoinitiator in photocuring field

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
VON RICHTHOFEN ANDREAS A., MARZORATI LILIANA, DUCATI LUCAS C., DI VITTA CLAUDIO: "Synthesis and Diels–Alder Reactions of a Benzo[5]radialene Derivative", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 16, no. 15, 1 August 2014 (2014-08-01), US, pages 4020 - 4023, XP055822096, ISSN: 1523-7060, DOI: 10.1021/ol5018432 *

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