WO2017177797A1 - 一种新型阳离子光固化体系及其组合物的应用 - Google Patents

一种新型阳离子光固化体系及其组合物的应用 Download PDF

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WO2017177797A1
WO2017177797A1 PCT/CN2017/077369 CN2017077369W WO2017177797A1 WO 2017177797 A1 WO2017177797 A1 WO 2017177797A1 CN 2017077369 W CN2017077369 W CN 2017077369W WO 2017177797 A1 WO2017177797 A1 WO 2017177797A1
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group
photocurable composition
composition according
cationic
ether
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PCT/CN2017/077369
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English (en)
French (fr)
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钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Publication of WO2017177797A1 publication Critical patent/WO2017177797A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the invention belongs to the technical field of organic light curing, and in particular relates to a cationic photocurable composition and its application in the field of photocuring.
  • Cationic photocuring has the characteristics of less oxygen inhibition, less volume shrinkage during curing, favorable substrate adhesion, strong post-cure, low odor, etc., and has received more and more attention in the field of photocuring.
  • the initiating light source of existing cationic photocuring systems is dominated by high pressure mercury lamps (typically in the range of 200-360 nm).
  • high pressure mercury lamps typically in the range of 200-360 nm.
  • the practical application shows that most of the existing cationic photocuring systems have low quantum absorption rate, low photocuring rate and incomplete curing under high pressure mercury lamps. Only a few systems with good curing effects have complex components and high cost. insufficient.
  • high-pressure mercury lamps have high energy consumption, large environmental pollution, and are increasingly restricted in their use.
  • LED light sources typically in the range of 320-500 nm
  • existing cationic photocuring systems have a poorer absorption capacity for LED light sources and are often difficult to cure.
  • the composition has low cost, excellent response to light sources in the wavelength range of 200-500 nm, fast curing speed, good developability and pattern integrity, and high hardness of the cured film on the substrate. Strong adhesion on the top.
  • the cationic photocurable composition of the present invention comprises the following components:
  • R 1 and R 2 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C 40 linear or branched alkyl, C 1 -C 40 alkoxy, or -O-CO-R a group, and at least one of R 1 and R 2 is a -O-CO-R group, R represents a C 3 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group or a cycloalkyl group An alkyl group, a C 2 -C 40 ester-containing group, a C 2 -C 40 -containing epoxy group, a halogen, or a C 3 -C 20 halogen-substituted alkyl group;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C 40 linear or branched alkyl a C 3 -C 40 cycloalkyl group, a C 4 -C 40 alkylcycloalkyl group or a cycloalkylalkyl group, a C 2 -C 40 alkenyl group, or a C 6 -C 40 aryl group, and
  • the acyclic -CH 2 - in these groups may be optionally substituted by -O-, -CO-, -NH-, -S- or 1,4-phenylene;
  • the cationic photocurable composition of the present invention has a good response to light in the wavelength range of 200-500 nm.
  • Suitable light sources include, but are not limited to, mercury lamps, halogen lamps, electrodeless lamps, LED lamps, lasers, and the like.
  • the photocurable composition of the present invention can be applied to paints, coatings, inks and molding materials, and can be specifically applied to: in plastics, metals, glass, ceramics, wood, walls, optical fibers, and the like.
  • Coating materials for coating protective coating materials such as hard coating agent, antifouling film, antireflection film, impact buffer film; photocurable adhesive, adhesive, photodegradable coating, coating film, molding; holographic image Optical recording medium for materials, etc.
  • optical molding resin for example, 3D printing ink (resin), photoresist for electronic circuit and semiconductor manufacturing, photoresist for electronic materials such as color filter, black matrix, dry film, etc.
  • interlayer insulating film interlayer insulating film, light extraction film, brightness enhancement film, sealing material; printing ink for screen printing, offset printing, gravure printing, photocuring ink for inkjet printing; lens, lens array, optical waveguide, guide Optical components such as light plates, light diffusing plates, and diffractive elements; optical spacers, rib walls, materials for nanoimprinting, and the like.
  • the components of the cationic photocurable composition of the present invention mainly comprise components (A), (B) and (C), all of which belong to the class of compounds known in the prior art.
  • the cationic photocurable composition has excellent response to light sources (such as mercury lamps and LED lamps) in the wavelength range of 200-500 nm, fast curing speed, excellent developability and pattern integrity.
  • the cured film has high hardness, strong adhesion on the substrate, low cost, and superior application effect.
  • the photocurable composition of the present invention mainly comprises components (A) to (C), and the components will be described in more detail below.
  • the oxime ester sensitizer of the component (A) is selected from a compound having a structure represented by the formula (I) and/or a macromolecular compound having a main structure of the compound of the formula (I):
  • R 1 and R 2 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C 40 linear or branched alkyl, C 1 -C 40 alkoxy, or -O-CO-R a group, and at least one of R 1 and R 2 is a -O-CO-R group, R represents a C 3 -C 20 cycloalkyl group, a C 4 -C 20 alkylcycloalkyl group or a cycloalkyl group An alkyl group, a C 2 -C 40 ester-containing group, a C 2 -C 40 -containing epoxy group, a halogen, or a C 3 -C 20 halogen-substituted alkyl group;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C 40 linear or branched alkyl a C 3 -C 40 cycloalkyl group, a C 4 -C 40 alkylcycloalkyl group or a cycloalkylalkyl group, a C 2 -C 40 alkenyl group, or a C 6 -C 40 aryl group, and
  • the acyclic -CH 2 - in these groups may be optionally substituted by -O-, -CO-, -NH-, -S- or 1,4-phenylene.
  • the non-cyclic -CH 2 - means that no cyclic structure in -CH 2 -, i.e. exclude cyclic structure -CH 2 -.
  • the above R "acyclic 2 -CH -" 3 -R 10 in 2 includes straight chain or branched chain alkyl -CH - alkyl structure, alkylcycloalkyl and cycloalkylalkyl in -CH 2 -, alkenyl and -CH 2 - in aryl.
  • R 1 and R 2 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C 20 linear or branched alkyl, C 1 -C Alkoxy group of 20 , or -O-CO-R group, and at least one of R 1 and R 2 is a -O-CO-R group, and R represents a C 3 -C 10 cycloalkyl group, C 4 -C 14 alkylcycloalkyl or cycloalkylalkyl, C 3 -C 20 ester-containing group, C 3 -C 20 epoxy group-containing group, halogen, or C 3 -C 20 An alkyl group substituted by a halogen.
  • the ester group-containing group means that the group contains at least one -CO-O- or -O-CO-, and for example, may be a group containing a (meth) acrylate group.
  • the other structural moiety containing the ester group is an alkyl structure and/or an alkenyl structure in addition to the ester group.
  • the epoxy group-containing group means that the group contains at least one epoxy group; preferably, in addition to the epoxy group, the other structural moiety of the epoxy group is an alkyl structure. .
  • R 1 and R 2 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C 10 linear or branched alkyl, C 1 -C 10 alkoxy, or -O-CO-R group, and at least one of R 1 and R 2 is a -O-CO-R group, and R is selected from one of the following groups:
  • C k H 2k+1 , C n H 2n+1 , C z H 2z+1 and C q H 2q+1 represent a linear or branched alkyl group having a corresponding number of carbon atoms;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represent hydrogen, nitro, cyano, halogen, C 1 -C straight or branched 20 alkyl group, C 3 -C 20 cycloalkyl, C 4 -C 20 alkylcycloalkyl or cycloalkylalkyl, C 2 -C 10 alkenyl is Or a C 6 -C 20 aryl group, and the acyclic -CH 2 - of these groups may be optionally substituted by -O-, -CO- or 1,4-phenylene.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each independently represent a straight chain of hydrogen, nitro, cyano, halogen, C 1 -C 12 or Branched alkyl, C 3 -C 10 cycloalkyl, C 4 -C 10 alkylcycloalkyl or cycloalkylalkyl, C 2 -C 6 alkenyl, or C 6 -C 10
  • An aryl group, and the acyclic -CH 2 - in these groups may be optionally substituted by -O- or -CO-.
  • a compound having a structure represented by the formula (I) can be obtained commercially or conveniently obtained by a conventionally known method.
  • the preparations can be referred to the methods described in CN104991418A, CN105001081A, CN105037587A, and JP2013107848A, which are hereby incorporated by reference in entirety.
  • the macromolecular compound having the main structure of the compound of the formula (I) may be a compound of the formula (I) by polymerization (including homopolymerization and copolymerization), esterification or transesterification. And the formation of macromolecular compounds.
  • polymerization including homopolymerization and copolymerization
  • esterification or transesterification.
  • the corresponding synthetic methods can be found in the Chinese Patent Application Publication No. WO104991418A, the disclosure of which is incorporated herein by reference.
  • the oxime ester sensitizer as the component (A) may be one or a combination of two or more of the compounds shown by the following structures:
  • the oxime ester sensitizer as the component (A) may be one or a combination of two or more compounds selected from the group consisting of the structure represented by the formula (I).
  • the content of the component (A) oxime ester sensitizer in the composition is from 0.001 to 10%, preferably from 0.01 to 5%, more preferably from 0.1 to 2% by mass.
  • the cationically reactive compound as the component (B) is an epoxy group-containing compound and/or an alkenyl ether group-containing compound.
  • the compound may be in the form of a monomer, a prepolymer, an oligomer, a polymer or the like.
  • the epoxy group-containing compound is preferably a glycidyl ether epoxy resin, a glycidyl ester epoxy resin, a glycidylamine epoxy resin, a linear aliphatic epoxy resin, an aliphatic epoxy resin, and an oxa compound.
  • a glycidyl ether epoxy resin preferably a glycidyl ester epoxy resin, a glycidylamine epoxy resin, a linear aliphatic epoxy resin, an aliphatic epoxy resin, and an oxa compound.
  • the epoxy group-containing compound is further preferably glycidol such as a bisphenol A type epoxy resin or an aliphatic glycidyl ether resin, from the viewpoints of compatibility effects such as curing efficiency, developability, film hardness, and substrate adhesion.
  • glycidol such as a bisphenol A type epoxy resin or an aliphatic glycidyl ether resin
  • compatibility effects such as curing efficiency, developability, film hardness, and substrate adhesion.
  • the epoxy group-containing compound may be 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate or bis(ethylene bromide) (3,4-epoxycyclohexyl) Ester), trimethylolpropane glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, 2,2'-[(1-methylethylidene)bis(4,1-phenylene) Base formaldehyde)] homopolymer of dioxirane (bisphenol A type epoxy resin), 3-oxiranyl 7-oxabicyclo[4,1,0]heptane, ethylene glycol double Glycidyl ether, C 12 -C 14 alkyl glycidyl ether, 3-methyl-3-vinyl hydroxymethyl oxetane, 3-methyl-3-vinyl hydroxy polyethoxylated methyl oxalate Cyclobutane, 1,4-bis(
  • the alkenyl ether may be one or more selected from the group consisting of vinyl ether, 1-propenyl ether, 1-butenyl ether, and 1-pentenyl ether. It is preferably a vinyl ether. More preferably, the vinyl ether group-containing compound may be selected from the group consisting of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerin carbonate vinyl One or a combination of two or more of ether, dodecyl vinyl ether and the like.
  • the content of the component (B) cationically reactive compound is from 10 to 90%, preferably from 40 to 90% by mass.
  • the component (C) cationic photoinitiator may be one or more of an aryldiazonium salt, an iodonium salt, a sulfonium salt, and an arylferrocene salt. The combination.
  • the component (C) is preferably an iodonium salt and a sulfonium salt, and particularly preferably has the following formula (II) and/or (III), based on consideration of cost, effect of use in combination, such as photoinitiation efficiency, curing speed, and the like. Structure of the compound:
  • R 11 and R 12 each independently represent hydrogen, a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkylalkyl group or an alkylcycloalkyl group, and among these groups Acyclic-CH 2 - may be optionally substituted by -O-, -S- or 1,4-phenylene;
  • R 13 and R 14 each independently represent hydrogen, C 1 -C 20 linear or branched alkyl, C 4 -C 20 cycloalkylalkyl or alkylcycloalkyl, or C 6 -C 20
  • An aryl group, and acyclic-CH 2 - in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;
  • R 15 represents a C 6 -C 20 aryl group, a C 1 -C 20 linear or branched alkyl group, a C 4 -C 20 cycloalkylalkyl group or an alkylcycloalkyl group, substituted or unsubstituted a phenylthiophenyl group, and the acyclic -CH 2 - of these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;
  • X in the formula (II) and the formula (III) each independently represents PF 6 - , SbF 6 - , CF 3 SO 3 - , C 4 F 9 SO 3 - , C 8 F 17 SO 3 - , (SO 2 C 4 F 9 ) 2 N - or B(C 6 M 5 ) 4 - (M stands for H, F, Cl, Br).
  • R 11 and R 12 each independently represent hydrogen, a C 1 -C 12 linear or branched alkyl group, a C 4 -C 10 cycloalkylalkyl group or an alkylcycloalkyl group, and a non- Ring-CH 2 - may be optionally substituted by -O-;
  • R 13 and R 14 each independently represent hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 4 -C 10 cycloalkylalkyl group or an alkylcycloalkyl group, a C 6 -C 12 aryl group.
  • the acyclic -CH 2 - in these groups may be optionally substituted by -O-, -S- or 1,4-phenylene;
  • R 15 represents a C 6 -C 10 aryl group, a substituted or unsubstituted phenylthiophenyl group, and a non-cyclic -CH 2 - of these groups may be optionally -O-, -S- or 1 Substituted by 4-phenylene.
  • the above iodonium salt and sulfonium salt may be exemplified by the following structure:
  • cationic photocurable composition of the present invention when two or more cationic photoinitiators are selected, they may be a combination of two or more of the same type (such as an iodonium salt or a sulfonium salt), or may be different. A combination of class compounds.
  • the component (C) cationic photoinitiator is contained in the composition in an amount of from 0.001 to 20%, preferably from 0.1 to 10% by mass.
  • the photocurable composition of the present invention may optionally be added with organic and/or inorganic auxiliaries commonly used in the art, including but It is not limited to pigments, leveling agents, dispersants, curing agents, surfactants, solvents, etc., as will be apparent to those skilled in the art.
  • organic and/or inorganic auxiliaries commonly used in the art, including but It is not limited to pigments, leveling agents, dispersants, curing agents, surfactants, solvents, etc., as will be apparent to those skilled in the art.
  • other sensitizers and/or photoinitiators may be added to the composition for compounding without adversely affecting the application of the composition.
  • one or more macromolecules or polymer compounds may be selectively added to the composition to improve the application performance of the composition during use.
  • the macromolecular or high molecular compound may be a polyol or Polyester polyols, etc.
  • the photocurable composition of the present invention can be obtained by weighing each component by weight and uniformly mixing.
  • the invention is optimized by components, especially the addition of a specific oxime sensitizer, so that the photocurable composition has a large wavelength range of light and good light curing effect, and can be applied in various fields such as paints, coatings, inks, molding materials and the like. , with strong technology and market competitiveness.
  • the photocurable composition was formulated according to the formulation shown in Table 1 below.
  • the photocurable composition was stirred under a yellow light, and a film was formed by roll-coating on a PET template, and dried at 90 ° C for 5 minutes to remove a solvent to form a coating film having a film thickness of about 2 ⁇ m.
  • the substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and the coating film was exposed to light with a high pressure mercury lamp (exposure model RW-UV70201, light intensity: 50 mW/cm 2 ) for an exposure time of 30 s. Visual observation was performed to evaluate the film formation of the exposed area.
  • the evaluation criteria for film formation are as follows:
  • ⁇ the surface of the film is smooth
  • the developability evaluation criteria are as follows:
  • the pattern integrity evaluation criteria are as follows:
  • the photocurable composition was stirred under a yellow light, and a film was formed by roll-coating on a PET template, and dried at 90 ° C for 5 minutes to remove a solvent to form a coating film having a film thickness of about 2 ⁇ m.
  • the substrate on which the coating film was formed was cooled to room temperature, and a mask was attached thereto.
  • the LED light source having a wavelength of 395 nm and a light intensity of 2300 mW/cm 2 was used to maintain the distance between the substrate on which the coating film was formed and the tube at 10 cm, and exposed and detected. Its initial curing time.
  • the initial curing time refers to the time when the surface hardness of the material reaches the trace without using the 1H Zhonghua advanced drawing pencil under the illumination of the LED light source.
  • the preliminary curing time can be used to measure the initiation efficiency of the photoinitiator.
  • Example 1 Taking the photocurable composition of Example 1 as a representative, refer to the "Scratch Test of Paint and Paint Film of GBT9286-1998", using the QFH knife-cutting method, using the QFH paint film scribing method, the photocurable composition is Adhesion on different substrates was tested.
  • the photocurable composition is uniformly applied to different substrates and cured under a high pressure mercury lamp and an LED lamp source respectively (the application conditions and the curing conditions are as described in the above (1) and (2), without using a mask, high pressure Exposure to mercury lamp for 30s, exposure to LED light source for 2s), aging after standing at room temperature for 24h, then use a 100-blade knife to cut 100 squares in the horizontal and vertical directions to form 100 small squares, then use the brush diagonal direction Brush each time five times, use 3M600 tape to stick on the incision and pull it again, with a magnifying glass
  • the degree of adhesion of the coating film to the substrate was evaluated by evaluating the integrity of the coating film in the square. The more complete the coating in the square, the stronger the adhesion.
  • the evaluation criteria are as follows:
  • edge of the slit is completely smooth, and the edge of the lattice is not peeled off;
  • the cationic photocurable composition of the present invention has good photocuring effect under mercury lamp and LED light source, high sensitivity, fast curing speed, developability and pattern integrity. Good, and the film hardness is high, showing strong adhesion on different substrates.
  • the present invention enables the photo-curing composition to have a large photosensitive wavelength range by component optimization, particularly the addition of a specific oxime ester sensitizer. It has good light curing effect and can be applied in many aspects such as paint, paint, ink and molding materials, and has strong technical and market competitiveness.

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Abstract

一种阳离子光固化组合物，包含：蒽酯类增感剂，选自具有式（Ⅰ）所示结构的化合物和/或以式（Ⅰ）化合物为主要结构的大分子化合物；阳离子反应型化合物；阳离子型光引发剂。相对于传统的阳离子光固化体系，该组合物成本低，对200-500nm波长范围内的光源具有极佳响应，固化速度快，显影性和图案完整性佳，且固化膜硬度高，在基材上的附着力强，能够在诸如油漆、涂料、油墨、成型材料等多方面得到应用。

Description

一种新型阳离子光固化体系及其组合物的应用 技术领域
本发明属于有机光固化技术领域，具体涉及一种阳离子光固化组合物及其在光固化领域中的应用。
背景技术
阳离子光固化具有不易氧阻聚、固化时体积收缩小、有利于基材附着、后固化强、气味低等特点，在光固化领域受到了越来越多的关注。与其它光固化体系一样，现有阳离子光固化体系的引发灯源以高压汞灯(波长范围通常为200-360nm)为主。然而实际应用表明，已有的大多数阳离子光固化体系在高压汞灯下量子吸收率小，光固化速率低，固化不完全，仅有的少数固化效果良好的体系也存在组分复杂、成本高等不足。此外，高压汞灯能耗高，环境污染大，使用也受到越来越多的限制。这些缺陷在极大程度上限制了阳离子光固化体系的推广应用。LED光源(波长范围通常为320-500nm)损害小、能量高、消耗低，被认为是能够替代汞灯以作为光固化体系中常规光源的良好替代品。然而，现有的阳离子光固化体系对LED光源的吸收能力更差，往往难以固化。有鉴于此，顺应当前技术发展趋势和实际应用需求，研发在200-500nm波长范围内(包括汞灯和LED光源)均具有优异光固化性能的阳离子光固化体系就显得尤为必要。
发明内容
针对现有技术的不足，本发明的目的在于提供一种新型阳离子光固化组合物。相对于传统的阳离子光固化体系，该组合物成本低，对200-500nm波长范围内的光源具有极佳响应，固化速度快，显影性和图案完整性佳，且固化膜硬度高，在基材上的附着力强。
具体来说，本发明的阳离子光固化组合物，包含以下组分：
(A)蒽酯类增感剂，选自具有式(I)所示结构的化合物和/或以式(I)化合物为主要结构的大分子化合物：
Figure PCTCN2017077369-appb-000001
R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C40的直链或支链烷基、C1-C40的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R代表C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C2-C40的含酯基基团、C2-C40的含环氧基基团、卤素、或C3-C20的被卤素取代的烷基；
R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C40的直链或支链烷基、C3-C40的环烷基、C4-C40的烷基环烷基或环烷基烷基、C2-C40的链烯基、或C6-C40的芳基，且这些基团中的非环-CH2-可任选地(optionally)被-O-、-CO-、-NH-、-S-或1,4-亚苯基所取代；
(B)阳离子反应型化合物；
(C)阳离子型光引发剂。
本发明的阳离子光固化组合物对200-500nm波长范围内的光都有很好的响应，适用光源包括(但不限于)汞灯、卤灯、无极灯、LED灯、激光等。
鉴于其优异的性能，本发明的光固化组合物能够应用在油漆、涂料、油墨和成型材料等方面，具体可应用于制作：在塑料、金属、玻璃、陶瓷、木材、墙体、光纤等基材上进行涂布的涂料；硬涂层剂、防污膜、防反射膜、冲击缓冲膜等保护膜材料；光固化黏合剂、黏着剂，光分解型涂料、涂膜、成型物；全息影像材料等的光记录介质；光学成型树脂，例如，3D打印用油墨(树脂)，电子电路和半导体制造用光刻胶，显示器中彩色滤光片、黑色矩阵、干膜等电子材料用光刻胶等；层间绝缘膜，光提取膜，增亮膜，密封材料；丝网印刷、胶板印刷、凹版印刷等印刷用油墨，喷墨打印用光固化油墨；镜片、透镜阵列、光导波路、导光板、光扩散板、衍射元件等光学部件；光间隙物，肋壁，纳米压印用材料；等等。
本发明阳离子光固化组合物的组分主要包括组分(A)、(B)和(C)，这三种组分均属于现有技术中的已知类别化合物。通过这三种组分的配合使用，该阳离子光固化组合物对200-500nm波长范围内的光源(如汞灯和LED灯)具有极佳响应，固化速度快，显影性和图案完整性优异，固化膜硬度高，在基材上的附着力强，且成本较低，应用效果优越。
本发明的光固化组合物主要包含组分(A)-(C)，以下将对各组分进行更加详细的说明。
<组分(A)蒽酯类增感剂>
作为组分(A)的蒽酯类增感剂，选自具有式(I)所示结构的化合物和/或以式(I)化合物为主要结构的大分子化合物：
Figure PCTCN2017077369-appb-000002
R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C40的直链或支链烷基、C1-C40的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R代表C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C2-C40的含酯基基团、C2-C40的含环氧基基团、卤素、或C3-C20的被卤素取代的烷基；
R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C40的直链或支链烷基、C3-C40的环烷基、C4-C40的烷基环烷基或环烷基烷基、C2-C40的链烯基、或C6-C40的芳基，且这些基团中的非环-CH2-可任选地被-O-、-CO-、-NH-、-S-或1,4-亚苯基所取代。
本文中，非环-CH2-是指不处于环状结构中的-CH2-，即排除环状结构中的-CH2-。例如，上述R3-R10中所述“非环-CH2-”包括直链或支链烷基中的-CH2-、烷基环烷基和环烷基烷基的烷基结构中的-CH2-、链烯基和芳基中的-CH2-。
作为优选方案，式(I)所示结构中，R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C20的直链或支链烷基、C1-C20的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R代表C3-C10的环烷基、C4-C14的烷基环烷基或环烷基烷基、C3-C20的含酯基基团、C3-C20的含环氧基基团、卤素、或C3-C20的被卤素取代的烷基。
在R的可选基团中，所述的含酯基基团是指基团中含有至少一个-CO-O-或-O-CO-，例如可以是含有(甲基)丙烯酸酯基的基团；优选地，除了酯基之外，所述含酯基基团的其他结构部分均属于烷基结构和/或链烯基结构。所述的含环氧基基团是指基团中含有至少一个环氧基团；优选地，除了环氧基团之外，所述含环氧基基团的其他结构部分均属于烷基结构。
进一步优选地，式(I)所示结构中，R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C10的直链或支链烷基、C1-C10的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R选自下列基团之一：
Figure PCTCN2017077369-appb-000003
其中h＝0-3，i＝1-4，且当h＝0时，环烷基上的氢可任选地被C1-C4烷基所取代；
-(CH2)j-CO-O-CkH2k+1或-(CH2)j-O-CO-CkH2k+1，其中j＝1-4，k＝1-6；
-(CH2)r-O-CO-CH＝CH2，其中r＝1-5；
Figure PCTCN2017077369-appb-000004
其中m＝1-3，n＝0-5；
Figure PCTCN2017077369-appb-000005
其中x＝1-3，y＝1-2，z＝0-3；
Figure PCTCN2017077369-appb-000006
其中p＝1-5，q＝0-5；
Cl、F、Br、-(CH2)s(CH2)tCCl、-(CH2)s(CH2)tCF、或-(CH2)s(CH2)tCBr，其中s＝1-6，t＝1-6；
且h、j、r、m、x、y、p、s、t所处结构中的氢可任选地被C1-C4烷基所取代。这些基团中，CkH2k+1、CnH2n+1、CzH2z+1和CqH2q+1代表具有相应碳原子数的直链或支链烷基；碳数的取值包括端值和端值之间的整数值，例如h＝0-3表示h可以是0、1、2或3；这些对于本领域技术人员而言是非常明确且显而易见的。
作为优选方案，式(I)所示结构中，R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C2-C10的链烯基、或C6-C20的芳基，且这些基团中的非环-CH2-可任选地被-O-、-CO-或1,4-亚苯基所取代。
进一步优选地，R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C12的直链或支链烷基、C3-C10的环烷基、C4-C10的烷基环烷基或环烷基烷基、C2-C6的链烯基、或C6-C10的芳基，且这些基团中的非环-CH2-可任选地被-O-或-CO-所取代。
本发明中，具有式(I)所示结构的化合物可通过商购获得或者经由现有已知方法方便地制得。例如，制备可参照CN104991418A、CN105001081A、CN105037587A、JP2013107848A中记载的方法，在此将其全文引入以作为参考。
作为可选的蒽酯类增感剂，所述的以式(I)化合物为主要结构的大分子化合物可以是式(I)化合物通过聚合(包括均聚和共聚)、酯化或酯交换反应而形成的大分子化合物。相应的合成方法可参照公开号为CN104991418A、CN105001081A的中国专利申请中记载的内容，在此将其全文引入以作为参考。
示例性地，作为组分(A)的蒽酯类增感剂可以是下列结构所示化合物中的一种或两种以上的组合：
Figure PCTCN2017077369-appb-000007
Figure PCTCN2017077369-appb-000008
Figure PCTCN2017077369-appb-000009
Figure PCTCN2017077369-appb-000010
Figure PCTCN2017077369-appb-000011
Figure PCTCN2017077369-appb-000012
在本发明的阳离子光固化组合物中，作为组分(A)的蒽酯类增感剂可以是一种或两种以上化合物的组合，所述化合物选自具有式(I)所示结构的化合物和/或以式(I)化合物为主要结构的大分子化合物。以质量百分比计，组分(A)蒽酯类增感剂在组合物中的含量为0.001-10％，优选0.01-5％，更优选0.1-2％。
<组分(B)阳离子反应型化合物>
作为组分(B)的阳离子反应型化合物为含有环氧基团的化合物和/或含有链烯基醚基团的化合物。化合物可以是单体、预聚物、低聚物、聚合物等化学形态。
含有环氧基团的化合物优选自缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、缩水甘油胺类环氧树脂、线性脂肪族类环氧树脂、脂肪族类环氧树脂和氧杂环丁烷类化合物中的一种或多种。
从配伍使用的效果如固化效率、显影性、膜硬度、基材附着力等因素考虑，上述含有环氧基团的化合物进一步优选双酚A型环氧树脂、脂肪族缩水甘油醚树脂等缩水甘油醚类环氧树脂、脂肪族类环氧树脂、和氧杂环丁烷类化合物中的一种或多种。
示例性地，含有环氧基团的化合物可以是3,4-环氧环己基甲基-3,4-环氧环己基甲酸酯、乙二酸双(3,4-环氧环己基甲酯)、三羟甲基丙烷缩水甘油醚、1,2-环氧-4-乙烯基环己烷、2,2'-[(1-甲基亚乙基)双(4,1-亚苯基甲醛)]双环氧乙烷的均聚物(双酚A型环氧树脂)、3-环氧乙烷基7- 氧杂二环[4,1,0]庚烷、乙二醇双缩水甘油醚、C12-C14烷基缩水甘油醚、3-甲基-3-乙烯羟甲基氧杂环丁烷、3-甲基-3-乙烯羟多乙氧基化甲基氧杂环丁烷、1,4-双(3-乙基-3-氧杂环丁烷基甲氧基)丁烷、1,6-双(3-乙基-3-氧杂环丁烷基甲氧基)己烷、季戊四醇三(3-乙基-3-氧杂环丁烷基甲基)醚、3-甲基-3-羟基甲基氧杂环丁烷、3-乙基-3-羟基甲基氧杂环丁烷、3-乙基-3-(2-乙基己氧基甲基)氧杂环丁烷、1,3-双[(3-乙基-3-氧杂环丁烷基甲氧基)甲基]丙烷、聚乙二醇双(3-乙基-3-氧杂环丁烷基甲基)醚、异丁氧基甲基(3-乙基-3-氧杂环丁烷基甲基)醚、乙二醇双(3-乙基-3-氧杂环丁烷基甲基)醚、三环癸烷二基二亚甲基(3-乙基-3-氧杂环丁烷基甲基)醚、三羟甲基丙烷三(3-乙基-3-氧杂环丁烷基甲基)醚、季戊四醇四(3-乙基-3-氧杂环丁烷基甲基)醚等中的一种或两种以上的组合。
上述含有链烯基醚基团的化合物中，链烯基醚可以是乙烯基醚、1-丙烯基醚、1-丁烯基醚、1-戊烯基醚等中的一种或多种，优选为乙烯基醚。更优选地，含有乙烯基醚基团的化合物可选自三甘醇二乙烯基醚、1,4-环己基二甲醇二乙烯基醚、4-羟丁基乙烯基醚、甘油碳酸酯乙烯基醚、十二烷基乙烯基醚等中的一种或两种以上的组合。
在本发明的阳离子光固化组合物中，以质量百分比计，组分(B)阳离子反应型化合物的含量为10-90％，优选40-90％。
<组分(C)阳离子型光引发剂>
在本发明的阳离子光固化组合物中，组分(C)阳离子型光引发剂可以是芳基重氮盐、碘鎓盐、硫鎓盐、芳基茂铁盐中的一种或两种以上的组合。
基于成本、配合使用的效果如光引发效率、固化速度等综合因素的考量，组分(C)优选碘鎓盐和硫鎓盐，特别优选具有如下式(II)和/或(III)所示结构的化合物：
Figure PCTCN2017077369-appb-000013
其中，R11和R12各自独立地代表氢、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或烷基环烷基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
R13和R14各自独立地代表氢、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或烷基环烷基、或C6-C20的芳基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
R15代表C6-C20的芳基、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或烷基环烷基、取代或未被取代的苯硫基苯基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
式(II)和式(III)中的X各自独立地代表PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、(SO2C4F9)2N-或B(C6M5)4 -(M代表H、F、Cl、Br)。
作为优选结构，式(II)和(III)所示结构的化合物中：
R11和R12各自独立地代表氢、C1-C12的直链或支链烷基、C4-C10的环烷基烷基或烷基环烷基，且这些基团中的非环-CH2-可任选地被-O-所取代；
R13和R14各自独立地代表氢、C1-C10的直链或支链烷基、C4-C10的环烷基烷基或烷基环烷基、C6-C12的芳基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
R15代表C6-C10的芳基、取代或未被取代的苯硫基苯基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代。
进一步优选地，上述碘鎓盐和硫鎓盐可列举出如下结构：
Figure PCTCN2017077369-appb-000014
Figure PCTCN2017077369-appb-000015
Figure PCTCN2017077369-appb-000016
在本发明的阳离子光固化组合物中，当选用两种以上阳离子型光引发剂时，可以是同一类(如碘鎓盐或硫鎓盐类)中的两种以上的组合，也可以是不同类别化合物的组合。以质量百分比计，组分(C)阳离子型光引发剂在组合物中的含量为0.001-20％，优选0.1-10％。
<组分(D)其他组分>
除了上述组分(A)、(B)和(C)外，根据产品应用需要，本发明的光固化组合物还可选择性地添加本领域中常用的有机和/或无机助剂，包括但不限于颜料、流平剂、分散剂、固化剂、表面活性剂、溶剂等，这对本领域技术人员而言是显而易见的。此外，在不对组合物应用效果产生负面影响的前提下，组合物中也可加入其它增感剂和/或光引发剂以复配使用。
根据应用需要，该组合物中还可选择性地添加一种或多种大分子或高分子化合物来提高组合物在使用过程中的应用性能，这种大分子或高分子化合物可以是多元醇或聚酯多元醇等。
<光固化组合物的制备>
将各组分按量称取后混合均匀即可获得本发明的光固化组合物。
现阶段阳离子光固化领域的市售产品以进口为主，这些产品大多拥有专利技术，产品价格高，而国内企业缺乏核心技术和自主知识产权，在严密的技术壁垒下，企业发展乃至研发布局都受到了极大限制。本发明通过组分优化，尤其是特定蒽酯增感剂的加入，使得光固化组合物的感光波长范围大，光固化效果好，能够在诸如油漆、涂料、油墨、成型材料等多方面得到应用，具有较强的技术和市场竞争力。
具体实施方式
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。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
如无特别说明，下文中所述份数均为重量份。各缩写的指代含义如下：
A1：
Figure PCTCN2017077369-appb-000017
A2：
Figure PCTCN2017077369-appb-000018
A3：
Figure PCTCN2017077369-appb-000019
A4：
Figure PCTCN2017077369-appb-000020
B1：双酚A环氧树脂(DGEBA)
B2：4-羟丁基乙烯基醚(HBVE)
B3：3,4-环氧环己基甲基-3,4-环氧环己基甲酸酯
B4：三甘醇二乙烯基醚
C1：
Figure PCTCN2017077369-appb-000021
C2:
Figure PCTCN2017077369-appb-000022
1、光固化组合物配制
按下表1中所示配方配制光固化组合物。
表1
Figure PCTCN2017077369-appb-000023
2、性能测试
(1)高压汞灯下成膜测试
将光固化组合物在黄光灯下搅拌，取料于PET模板上滚涂成膜,在90℃下干燥5min除去溶剂，形成膜厚约2μm的涂膜。将形成有涂膜的基板冷却至室温，附上掩膜板，用高压汞灯(曝光机型号RW-UV70201，光强50mW/cm2)照射对涂膜进行曝光，曝光时间30s。肉眼观察以评价曝光区域的成膜情况。
随后于25℃温度下在1％的NaOH水溶液中浸渍30s显影，再用超纯水洗涤，风干；接着在240℃的烘箱中后烘烤30min，得到掩膜板转移的图案。用扫描电子显微镜(SEM)观察基板上图案，以评价显影性和图案完整性。
成膜情况评价标准如下：
○：膜表面光滑；
◎：膜表面有瑕疵；
●：无法成膜。
显影性评价标准如下:
○：在未曝光部分未观察到残留物；
◎：在未曝光部分观察到少量残留物，但残留量可以接受；
●：在未曝光部分观察到明显残留物。
图案完整性评价标准如下:
○：没有观察到图案缺陷；
◎：观察到小部分图案有些许缺陷；
●：明显观察到许多图案缺陷。
评价结果如表2中所示。
表2
Figure PCTCN2017077369-appb-000024
Figure PCTCN2017077369-appb-000025
注：“-”是因为无法成膜，导致无法评价。
(2)LED光源下成膜测试
将光固化组合物在黄光灯下搅拌，取料于PET模板上滚涂成膜,在90℃下干燥5min除去溶剂，形成膜厚约2μm的涂膜。将形成有涂膜的基板冷却至室温，附上掩膜板，采用波长395nm、光强2300mW/cm2的LED光源，将形成有涂膜的基板与灯管距离保持在10cm，进行曝光并检测其初步固化时间。
初步固化时间是指在LED光源照射下，材料表面硬度达到用1H中华牌高级绘图铅笔刻画不出现痕迹的时间，该初步固化时间可用来衡量光引发剂的引发效率。
初步固化后，进行与上述(1)中相同的显影和后烘烤步骤，并采用相同的标准评价其显影性和图案完整性。
测试结果如下表3所示。
表3
Figure PCTCN2017077369-appb-000026
(3)基材附着力测试
以实施例1的光固化组合物为代表，参照《GBT9286-1998色漆和清漆漆膜的划痕实验》，采用百格划刀法，利用QFH漆膜划格仪，对光固化组合物在不同基材上的附着力进行测试。
具体方法如下：
将光固化组合物均匀涂抹于不同的基材上，分别在高压汞灯和LED灯源下固化(涂抹及固化条件如上述(1)和(2)中所述，不使用掩膜板，高压汞灯下曝光30s，LED光源下曝光2s)，固化完成后室温放置24h进行老化，然后使用百格刀横向与纵向各划1刀以形成100个细小方格，接着用毛刷对角线方向各刷五次，用3M600号胶带贴在切口上再拉开，用放大镜 观察格子区域的情况，通过评定方格内涂膜的完整程度来评定涂膜对基材附着程度。方格内涂膜越完整，表示附着能力越强。
评价标准如下：
A：切口的边缘完全光滑，格子边缘没有任何剥落；
B：在切口的相交处有小片剥落，划格区内实际破损≤5％；
C：切口的边缘和/或相交处有剥落，其面积5％-30％(不含5％)；
D：沿切口边缘有部分剥落或整大片剥落或全部剥落，或部分格子被整片剥落。剥落的面积超过30％。
评价结果如下表4所示。
表4
Figure PCTCN2017077369-appb-000027
结合表2-4的测试结果可以看出，本发明的阳离子光固化组合物在汞灯和LED光源下都具有很好的光固化效果，感光度高，固化速度快，显影性和图案完整性好，且涂膜硬度高，在不同基材上均表现出很强的附着力。
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：本发明通过组分优化，尤其是特定蒽酯增感剂的加入，使得光固化组合物的感光波长范围大，光固化效果好，能够在诸如油漆、涂料、油墨、成型材料等多方面得到应用，具有较强的技术和市场竞争力。
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。

Claims (20)

  1. 一种阳离子光固化组合物，其特征在于，包含以下组分：
    (A)蒽酯类增感剂，选自具有式(I)所示结构的化合物和/或以式(I)化合物为主要结构的大分子化合物：
    Figure PCTCN2017077369-appb-100001
    R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C40的直链或支链烷基、C1-C40的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R代表C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C2-C40的含酯基基团、C2-C40的含环氧基基团、卤素、或C3-C20的被卤素取代的烷基；
    R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C40的直链或支链烷基、C3-C40的环烷基、C4-C40的烷基环烷基或环烷基烷基、C2-C40的链烯基、或C6-C40的芳基，且这些基团中的非环-CH2-可任选地被-O-、-CO-、-NH-、-S-或1,4-亚苯基所取代；
    (B)阳离子反应型化合物；
    (C)阳离子型光引发剂。
  2. 根据权利要求1所述的阳离子光固化组合物，其特征在于：式(I)所示结构中，R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C20的直链或支链烷基、C1-C20的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R代表C3-C10的环烷基、C4-C14的烷基环烷基或环烷基烷基、C3-C20的含酯基基团、C3-C20的含环氧基基团、卤素、或C3-C20的被卤素取代的烷基。
  3. 根据权利要求1或2所述的阳离子光固化组合物，其特征在于：在R的可选基团中，所述的含酯基基团是指基团中含有至少一个-CO-O-或-O-CO-，且除了酯基之外，所述含酯基基团的其他结构部分均属于烷基结构和/或链烯基结构。
  4. 根据权利要求1或2所述的阳离子光固化组合物，其特征在于：在R的可选基团中，所述的含环氧基基团是指基团中含有至少一个环氧基团，且除了环氧基团之外，所述含环氧基基团的其他结构部分均属于烷基结构。
  5. 根据权利要求1或2所述的阳离子光固化组合物，其特征在于：式(I)所示结构中，R1和R2各自独立地代表氢、硝基、氰基、卤素、C1-C10的直链或支链烷基、C1-C10的烷氧基、或-O-CO-R基团，且R1和R2中的至少一个是-O-CO-R基团，R选自下列基团之一：
    Figure PCTCN2017077369-appb-100002
    其中h＝0-3，i＝1-4，且当h＝0时，环烷基上的氢可任选地被C1-C4烷基所取代；
    -(CH2)j-CO-O-CkH2k+1或-(CH2)j-O-CO-CkH2k+1，其中j＝1-4，k＝1-6；
    -(CH2)r-O-CO-CH＝CH2，其中r＝1-5；
    Figure PCTCN2017077369-appb-100003
    其中m＝1-3，n＝0-5；
    Figure PCTCN2017077369-appb-100004
    其中x＝1-3，y＝1-2，z＝0-3；
    Figure PCTCN2017077369-appb-100005
    其中p＝1-5，q＝0-5；
    Cl、F、Br、-(CH2)s(CH2)tCCl、-(CH2)s(CH2)tCF、或-(CH2)s(CH2)tCBr，其中s＝1-6，t＝1-6；
    且h、j、r、m、x、y、p、s、t所处结构中的氢可任选地被C1-C4烷基所取代。
  6. 根据权利要求1所述的阳离子光固化组合物，其特征在于：式(I)所示结构中，R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的烷基环烷基或环烷基烷基、C2-C10的链烯基、或C6-C20的芳基，且这些基团中的非环-CH2-可任选地被-O-、-CO-或1,4-亚苯基所取代。
  7. 根据权利要求1或6所述的阳离子光固化组合物，其特征在于：式(I)所示结构中，R3、R4、R5、R6、R7、R8、R9、R10各自独立地代表氢、硝基、氰基、卤素、C1-C12的直链或支链烷基、C3-C10的环烷基、C4-C10的烷基环烷基或环烷基烷基、C2-C6的链烯基、或C6-C10的芳基，且这些基团中的非环-CH2-可任选地被-O-或-CO-所取代。
  8. 根据权利要求1所述的阳离子光固化组合物，其特征在于：作为组分(B)的阳离子反应型化合物为含有环氧基团的化合物和/或含有链烯基醚基团的化合物。
  9. 根据权利要求8所述的阳离子光固化组合物，其特征在于：所述含有环氧基团的化合物选自缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、缩水甘油胺类环氧树脂、线性脂肪族类环氧树脂、脂肪族类环氧树脂和氧杂环丁烷类化合物。
  10. 根据权利要求8或9所述的阳离子光固化组合物，其特征在于：所述含有环氧基团的化合物选自缩水甘油醚类环氧树脂、脂肪族类环氧树脂和氧杂环丁烷类化合物。
  11. 根据权利要求8所述的阳离子光固化组合物，其特征在于：所述含有链烯基醚基团的化合物中，链烯基醚是乙烯基醚、1-丙烯基醚、1-丁烯基醚、或1-戊烯基醚，优选为乙烯基醚。
  12. 根据权利要求11所述的阳离子光固化组合物，其特征在于：所述含有乙烯基醚基团的化合物选自三甘醇二乙烯基醚、1,4-环己基二甲醇二乙烯基醚、4-羟丁基乙烯基醚、甘油碳酸酯乙烯基醚、十二烷基乙烯基醚中的一种或两种以上的组合。
  13. 根据权利要求1所述的阳离子光固化组合物，其特征在于：组分(C)阳离子型光引发剂是芳基重氮盐、碘鎓盐、硫鎓盐、芳基茂铁盐中的一种或两种以上的组合。
  14. 根据权利要求13所述的阳离子光固化组合物，其特征在于：组分(C)阳离子型光引发剂是碘鎓盐和/或硫鎓盐。
  15. 根据权利要求13或14所述的阳离子光固化组合物，其特征在于：组分(C)阳离子型光引发剂选自具有如下式(II)和/或(III)所示结构的化合物：
    Figure PCTCN2017077369-appb-100006
    其中，R11和R12各自独立地代表氢、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或烷基环烷基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
    R13和R14各自独立地代表氢、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或烷基环烷基、或C6-C20的芳基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
    R15代表C6-C20的芳基、C1-C20的直链或支链烷基、C4-C20的环烷基烷基或烷基环烷基、取代或未被取代的苯硫基苯基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
    式(II)和式(III)中的X各自独立地代表PF6 -、SbF6 -、CF3SO3 -、C4F9SO3 -、C8F17SO3 -、(SO2C4F9)2N-或B(C6M5)4 -，且其中B(C6M5)4 -中的M代表H、F、Cl、Br。
  16. 根据权利要求15所述的阳离子光固化组合物，其特征在于：
    R11和R12各自独立地代表氢、C1-C12的直链或支链烷基、C4-C10的环烷基烷基或烷基环烷基，且这些基团中的非环-CH2-可任选地被-O-所取代；
    R13和R14各自独立地代表氢、C1-C10的直链或支链烷基、C4-C10的环烷基烷基或烷基 环烷基、或C6-C12的芳基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代；
    R15代表C6-C10的芳基、取代或未被取代的苯硫基苯基，且这些基团中的非环-CH2-可任选地被-O-、-S-或1,4-亚苯基所取代。
  17. 根据权利要求8所述的阳离子光固化组合物，其特征在于：所述含有环氧基团的化合物选自缩水甘油醚类环氧树脂、缩水甘油酯类环氧树脂、缩水甘油胺类环氧树脂、线性脂肪族类环氧树脂、脂肪族类环氧树脂和氧杂环丁烷类化合物中的一种或多种。
  18. 根据权利要求8或9所述的阳离子光固化组合物，其特征在于：所述含有环氧基团的化合物选自缩水甘油醚类环氧树脂、脂肪族类环氧树脂和氧杂环丁烷类化合物中的一种或多种。
  19. 权利要求1-18中任一项所述的阳离子光固化组合物在光固化领域中的应用。
  20. 根据权利要求19所述的应用，其特征在于：所述光固化领域包括油漆、涂料、油墨和成型材料。
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