WO2018028461A1 - 一种新型阳离子型光引发剂及其制备方法和应用 - Google Patents

一种新型阳离子型光引发剂及其制备方法和应用 Download PDF

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WO2018028461A1
WO2018028461A1 PCT/CN2017/095371 CN2017095371W WO2018028461A1 WO 2018028461 A1 WO2018028461 A1 WO 2018028461A1 CN 2017095371 W CN2017095371 W CN 2017095371W WO 2018028461 A1 WO2018028461 A1 WO 2018028461A1
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cationic photoinitiator
optionally
cycloalkyl
oco
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PCT/CN2017/095371
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English (en)
French (fr)
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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 to KR1020197001265A priority Critical patent/KR102206574B1/ko
Priority to EP17838591.0A priority patent/EP3498691B1/en
Priority to JP2019501977A priority patent/JP6741854B2/ja
Priority to US16/318,890 priority patent/US10995082B2/en
Publication of WO2018028461A1 publication Critical patent/WO2018028461A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C07D335/14—Thioxanthenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 9
    • C07D335/16—Oxygen atoms, e.g. thioxanthones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/12—Sulfonium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/10—Dibenzothiopyrans; Hydrogenated dibenzothiopyrans
    • C07D335/12—Thioxanthenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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 particularly relates to a novel cationic photoinitiator and a preparation method and application thereof.
  • Photoinitiators are a key component of photocurable products and play a decisive role in the cure rate of photocurable products.
  • Photoinitiators can be divided into cationic photoinitiators and free radical photoinitiators according to their initiation mechanism. Compared with free radical polymerization, cationic photocuring systems have less oxygen inhibition and volume shrinkage during curing. Small, resin selection type is wider and more. In China, the research and development of cationic photocuring systems is relatively late, and there are not many enterprises capable of industrial production.
  • Triarylsulfonium salt is one of the most widely used and best-performing cationic photoinitiators. It is superior to diaryliodonium salts in terms of absorption wavelength, thermal stability and initiation activity, but such photoinitiators
  • the maximum absorption wavelength of the agent is still less than 300 nm, and the long-wavelength light source cannot be effectively utilized, and the solubility and migration problems are present, which limits the use to some extent.
  • People have tried to improve its structure, such as introducing long-chain alkyl groups to improve its solubility, introducing polyfunctional groups to improve the efficiency of initiation and thermal stability, etc. However, in practical applications, these improved structures tend to migrate easily to small molecules. Compounds, yellowing and other defects, and the efficiency of initiation still needs to be further improved. To this end, the subject photoinitiator was developed.
  • the object of the present invention is firstly to provide a novel cationic photoinitiator. It has been found that, as described in the following, in combination with the sulfonium salt structure and the hydrazine structure, the obtained photoinitiator absorbs red light, has excellent sensitizing properties, and is characterized by difficulty in migration and yellowing resistance.
  • R 1 and R 2 independently of each other represent halogen, OH, CN, NO 2 , C 1 -C 20 linear or branched alkyl, C 3 -C 20 cycloalkyl, C 4 -C 20 cycloalkane Alkylalkyl, C 4 -C 20 alkylcycloalkyl, C 6 -C 40 aryl or heteroaryl, wherein -CH 2 - may be optionally -O-, -S-, -NH -, -CO-, -COO- or -OCO-;
  • n 1 and m 2 represent the number of R 1 and R 2 , respectively, and independently take an integer of 0 to 3;
  • R 4 and R 5 independently of each other represent hydrogen, a C 1 -C 10 linear or branched alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 12 cycloalkylalkyl group, C 4 - An alkylcycloalkyl group of C 12 wherein -CH 2 - may be optionally substituted by -O-, -S-, -CO-, -COO- or -OCO-; and optionally, R 4 and R 5 can be linked into a ring;
  • R 6 and R 7 may be the same or different, and each independently represents a phenyl group, a diphenyl sulfide group, a benzophenone group, a decyl group, a diphenyl ether group, an oxazolyl group, wherein hydrogen may be used.
  • a halogen, CN, NO 2 , or C 1 -C 8 alkyl group, and -CH 2 - in the C 1 -C 8 alkyl group may be optionally -O-, -S -, -CO-, -COO- or -OCO- is substituted; optionally, R 6 and R 7 may be linked into a ring;
  • R 3 represents a hydrogen, halogen, CN, NO 2 , R 8 , -CO-R 8 or S + (R 6 )(R 7 ) group;
  • R 8 represents a C 1 -C 10 linear or branched alkyl group a C 3 -C 10 cycloalkyl group, a C 4 -C 15 cycloalkylalkyl group, a C 6 -C 20 aryl group, a C 7 -C 20 arylalkyl group, wherein the cycloalkyl structure and H in the aryl structure may be optionally substituted by a C 1 -C 6 alkyl group, and -CH 2 - may be optionally -O-, -S-, -NH-, -CO-, -COO- Or replaced by -OCO-;
  • X - represents a non-nucleophilic anion
  • n 1 or 2.
  • R 1 and R 2 independently of each other represent a straight or branched chain of halogen, OH, CN, NO 2 or C 1 -C 10 .
  • n 1 and m 2 independently take an integer of 0-2. Further preferably, both m 1 and m 2 are 0.
  • R 4 and R 5 independently of each other represent hydrogen, a C 1 -C 8 linear or branched alkyl group, a C 3 -C 6 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, Wherein acyclic-CH 2 - may be optionally substituted by -O-, -S-, -CO-, -COO- or -OCO-; and optionally, R 3 and R 4 may be bonded to each other to form Cycloalkyl.
  • R 6 and R 7 independently of each other represent phenyl, diphenyl sulfide, benzophenone, fluorenyl, diphenyl ether, carbazolyl, wherein the hydrogen may be optionally CN, NO 2 or a C 1 -C 4 alkyl group, and -CH 2 - in the C 1 -C 4 alkyl group may be optionally -O-, -S-, -CO-, -COO - or -OCO- replaced.
  • R 6 and R 7 are independently of each other selected from the group consisting of:
  • R 6 and R 7 may also be bonded to each other to form a ring by a sulfur ion; preferably the following groups are formed:
  • R 3 represents a hydrogen, halogen, CN, NO 2 , R 8 , -CO-R 8 or S + (R 6 ) (R 7 ) group;
  • R 8 represents a linear or branched C 1 -C 6 An alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, a C 6 -C 10 aryl group, a C 7 -C 12 arylalkyl group, wherein a cycloalkane
  • the H in the base structure and the aryl structure may be optionally substituted by a C 1 -C 4 alkyl group, and the acyclic -CH 2 - may be optionally -O-, -S-, -NH-, -CO -, -COO- or -OCO-.
  • R 3 represents a S + (R 6 ) (R 7 ) group
  • it is bilaterally symmetric with the S + (R 6 ) (R 7 ) group on the other side.
  • X ⁇ is selected from the group consisting of C m F 2m+1 SO 3 - , BF 4 - , SbF 6 - , AsF 6 - , PF 6 - and B(C 6 Q 5 ) 4 - , wherein Q represents hydrogen or halogen, m is an integer from 1-8.
  • X - is selected from the group consisting of CF 3 SO 3 - , C 4 F 9 SO 3 - , C 8 F 17 SO 3 - , PF 6 - , AsF 6 - , SbF 6 - or B(C 6 H 5 ) 4 - , B(C 6 F 5 ) 4 - .
  • n is the same as the number of the S + (R 6 ) (R 7 ) group in the formula (I).
  • R 3 represents a S + (R 6 )(R 7 ) group
  • n takes 2; when R 3 does not represent a S + (R 6 )(R 7 ) group, n takes 1.
  • cationic photoinitiator of the present invention may be selected from the following structures:
  • the present invention also relates to a method for preparing a novel cationic photoinitiator represented by the above formula (I), and the reaction scheme is as follows:
  • R 3 represents a S + (R 6 )(R 7 ) group
  • R 3 ' represents hydrogen
  • R 3 ' R 3 ;
  • the raw material a and the raw material b are subjected to a Friedel-Craft reaction in an organic solvent under the action of aluminum trichloride or zinc chloride to synthesize an intermediate;
  • the intermediate is added to an organic solvent in which NaX or KX is dissolved, stirred until dissolved, and then stirred by adding deionized water to precipitate a solid, which is suction filtered and recrystallized to obtain a product; wherein X of NaX and KX is the above non-nucleophilic Sex anion.
  • the raw materials used are all known compounds in the prior art, and can be easily prepared commercially or by a known synthesis method.
  • the raw material a can be synthesized by a method disclosed in, for example, Chinese Patent Application No. 201010557275.7, 200910030326.8, 2015109373280.0, the entire disclosure of which is incorporated herein by reference.
  • steps (1) and (2) are conventional reactions in the art for synthesizing similar compounds.
  • the specific reaction conditions are readily ascertainable to those skilled in the art on the basis of the synthetic idea disclosed in the present invention.
  • the reaction temperature is usually -10 to 30 °C.
  • the organic solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.
  • the ion exchange reaction in the step (2) is carried out in a solvent system, and the organic solvent to be used is not particularly limited as long as it can dissolve the reaction raw material, is miscible with water, and has no adverse effect on the reaction, such as acetone, methyl ethyl ketone, methyl group. Isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol.
  • the reaction temperature is not particularly limited and may be room temperature.
  • the present invention also includes the use of the cationic photoinitiator represented by the above formula (I) in a photocurable composition.
  • the cationic photoinitiator or mixture thereof can be used directly in the formulation or in combination with other cationic photoinitiators.
  • the photocurable composition containing the cationic photoinitiator of the present invention may optionally further contain a known additive such as a solvent, a sensitizer, a pigment, a filler, an antifoaming agent, and a leveling agent as needed. And non-reactive resins.
  • the photoinitiator of the present invention can be applied to coatings, coating agents, photoresists, photosensitive materials, sealing materials, inks, adhesives, polarizing films, epoxy floors, and the like.
  • the photoinitiator is capable of matching longer absorption wavelengths during application, resulting in excellent solubility, low mobility and yellowing resistance.
  • the application properties of the photoinitiator represented by the formula (I) of the present invention are evaluated by formulating an exemplary photocurable composition, including photosensitivity, storage stability, migration, yellowing resistance and the like.
  • the photocurable composition was formulated according to the formulation shown in Table 2. First, a cationic photoinitiator is dissolved in a solvent of propylene carbonate, and then uniformly mixed with a cationically polymerizable monomer to prepare a photocurable composition.
  • the cationically polymerizable monomer is one or a combination of two or more of A1, A2 and A3:
  • A1 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester (CAS: 2386-87-0);
  • A2 bis(3,4-epoxycyclohexylmethyl) hexanoate (CAS: 3130-19-6);
  • A3 1,4-cyclohexanedimethanol divinyl ether (CAS: 17351-75-6).
  • the cationic photoinitiator is a cationic photoinitiator of the invention or as a comparative compound A and/or B.
  • the 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 the coating film was exposed to light by a high pressure mercury lamp (exposure machine model RW-UV70201, wavelength 200-500 nm, light intensity 100 mW/cm 2 ), exposure time 2 s, room temperature 2 min.
  • Exposure machine model RW-UV70201 exposure machine model 200-500 nm, light intensity 100 mW/cm 2
  • exposure time 2 s room temperature 2 min.
  • the pencil hardness of the cured film was observed (test method is referred to GB/T 6739-1986); the higher the pencil hardness, the better the photocurability of the composition, that is, the more excellent the sensitivity of the initiator.
  • ⁇ pencil hardness is 2H or more
  • the pencil hardness is 2B or less or the pencil hardness cannot be measured.
  • the 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 the coating film was exposed to light by a high pressure mercury lamp (exposure machine model RW-UV70201, wavelength: 200-500 nm, light intensity: 100 mW/cm 2 ), and the exposure time was 4 s. Cured film.
  • the 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 the coating film was exposed to light by a high pressure mercury lamp (exposure machine model RW-UV70201, wavelength: 200-500 nm, light intensity: 100 mW/cm 2 ), and the exposure time was 4 s. Cured film.
  • the light source was a high pressure mercury lamp (main wavelength 365 nm, whole machine power: about 2.2 KW), and the cured film was continuously irradiated for 6 hours to observe the yellowing of the cured film:
  • ⁇ colorless and transparent, the surface is smooth
  • ⁇ The surface is yellow or the viscosity is increased.
  • the photocurable composition obtained above was heated in an oven at 80 ° C for 24 hours under light shielding, and stored at room temperature for one month in the dark, and the viscosity of the composition before and after one month of heating was measured. The less the viscosity rises, the better the storage stability.
  • ⁇ viscosity change is less than 1.5 times
  • Example / Comparative Example Sensitivity Mobility Yellowing resistance Storage stability Example 19 ⁇ ⁇ ⁇ ⁇ Example 20 ⁇ ⁇ ⁇ ⁇ Example 21 ⁇ ⁇ ⁇ ⁇ Example 22 ⁇ ⁇ ⁇ ⁇ Example 23 ⁇ ⁇ ⁇ ⁇ Example 24 ⁇ ⁇ ⁇ ⁇ Example 25 ⁇ ⁇ ⁇ ⁇ Example 26 ⁇ ⁇ ⁇ ⁇ Example 27 ⁇ ⁇ ⁇ ⁇ Example 28 ⁇ ⁇ ⁇ ⁇ Example 29 ⁇ ⁇ ⁇ ⁇ Comparative example 1 ⁇ ⁇ ⁇ ⁇ Comparative example 2 ⁇ ⁇ ⁇ Comparative example 3 ⁇ ⁇ ⁇ ⁇ Comparative example 4 ⁇ ⁇ ⁇ ⁇ Comparative Example 5 ⁇ ⁇ ⁇ ⁇ ⁇
  • the photocurable composition using the cationic photoinitiator of the present invention is excellent in photographic performance compared to the conventional sulfonium salt photoinitiator (compounds A and B), and the pencil hardness of the cured film is uniform. It has more than 2H and is characterized by difficulty in migration, yellowing resistance and better storage stability.
  • the cationic photoinitiator used in Examples 19-29 has a larger molecular weight than the compound A or B, and the molar amount is relatively low at the same mass, and the pencil hardness is above 2H, further illustrating The photoinitiator of the present invention has advantages in photographic performance.

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Abstract

公开一种新型阳离子型光引发剂及其制备方法和应用。该阳离子型光引发剂具有如下通式(I)所示的结构，其在应用过程中能够匹配更长的吸收波长，感光性能优异，且具有不易迁移、耐黄变的特点。

Description

一种新型阳离子型光引发剂及其制备方法和应用 技术领域
本发明属于有机光固化技术领域，特别涉及一种新型阳离子型光引发剂及其制备方法和应用。
背景技术
光引发剂是光固化产品的关键组分，它对光固化产品的固化速率起着决定作用。光引发剂按照其引发机理的不同，可分为阳离子型光引发剂和自由基型光引发剂，与自由基聚合相比，阳离子型光固化体系具有受氧阻聚较小、固化时体积收缩小、树脂选用类型较宽泛等优点。在我国，阳离子型光固化体系的研究和开发较晚，能够工业化生产的企业不多。
三芳基硫鎓盐是目前应用最广泛、性能较好的一类阳离子型光引发剂，在吸收波长、热稳定性、引发活性等方面都优于二芳基碘鎓盐，但是这类光引发剂的最大吸收波长仍小于300nm，不能有效利用长波长光源，且存在溶解性及迁移性问题，在一定程度上限制了使用。人们设法对其结构进行改进，如引入长链烷基来提高其溶解性能，引入多官能团来提高引发效率及热稳定性等，但在实际应用中，这些改进的结构往往存在易迁移出小分子化合物、易黄变等缺陷，且引发效率仍然需要进一步提高。为此，题述的光引发剂被开发。
发明内容
针对现有技术的不足，本发明的目的首先在于提供一种新型阳离子型光引发剂。研究发现，如下文中所述那样结合硫鎓盐结构和芴类结构，所得的光引发剂吸收波长红移，感光性能优异，且具有不易迁移、耐黄变的特点。
为了达到上述技术效果，本发明采用的技术方案如下。
一种阳离子型光引发剂，其具有如通式(I)所示的结构：
Figure PCTCN2017095371-appb-000001
其中，
R1和R2相互独立地表示卤素、OH、CN、NO2、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C6-C40的芳基或杂芳基，其中的-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代；
m1和m2分别表示R1和R2的个数，相互独立地取0-3的整数；
R4和R5相互独立地表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C12的环烷基烷基、C4-C12的烷基环烷基，其中的-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代；并且任选地，R4和R5可链接成环；
R6和R7可相同，也可不同，两者相互独立地表示苯基、二苯硫醚基、二苯甲酮基、芴基、二苯醚基、咔唑基，其中的氢可任选地被卤素、CN、NO2、或C1-C8的烷基所取代，且所述C1-C8的烷基中的-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代；任选地，R6和R7可链接成环；
R3代表氢、卤素、CN、NO2、R8、-CO-R8或S+(R6)(R7)基团；R8表示C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C15的环烷基烷基、C6-C20的芳基、C7-C20的芳基烷基，其中，环烷基结构和芳基结构中的H可任选地被C1-C6的烷基所取代，-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代；
X-表示非亲核性阴离子；
n为1或2。
作为优选技术方案，上述通式(I)所示的阳离子型光引发剂中，R1和R2相互独立地表示卤素、OH、CN、NO2、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C12的环烷基烷基、C4-C12的烷基环烷基、C6-C20的芳基或杂芳基，其中的-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代。
优选地，m1和m2相互独立地取0-2的整数。进一步优选地，m1和m2均为0。
优选地，R4和R5相互独立地表示氢、C1-C8的直链或支链烷基、C3-C6的环烷基、C4-C10的环烷基烷基，其中的非环-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代；并且任选地，R3和R4可彼此相连以形成环烷基。
优选地，R6和R7相互独立地表示苯基、二苯硫醚基、二苯甲酮基、芴基、二苯醚基、咔唑基，其中的氢可任选地被CN、NO2、或C1-C4的烷基所取代，且所述C1-C4的烷基中的-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代。
进一步优选地，R6和R7相互独立地选自下列基团：
Figure PCTCN2017095371-appb-000002
R6和R7亦可彼此相连，通过硫离子成环；优选形成下列基团：
Figure PCTCN2017095371-appb-000003
优选地，R3代表氢、卤素、CN、NO2、R8、-CO-R8或S+(R6)(R7)基团；R8表示C1-C6的直链或支链烷基、C3-C8的环烷基、C4-C10的环烷基烷基、C6-C10的芳基、C7-C12的芳基烷基，其 中，环烷基结构和芳基结构中的H可任选地被C1-C4的烷基所取代，非环-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代。
进一步优选地，当R3表示S+(R6)(R7)基团时，它与另一侧的S+(R6)(R7)基团左右对称。
优选地，X-选自CmF2m+1SO3 -、BF4 -、SbF6 -、AsF6 -、PF6 -以及B(C6Q5)4 -，其中Q代表氢或卤素，m为1-8的整数。进一步优选地，X-选自CF3SO3 -、C4F9SO3 -、C8F17SO3 -、PF6 -、AsF6 -、SbF6 -或B(C6H5)4 -、B(C6F5)4 -。
n的取值与通式(I)中S+(R6)(R7)基团的数量相同。当R3表示S+(R6)(R7)基团时，n取2；当R3不表示S+(R6)(R7)基团时，n取1。
非限制性地，本发明的阳离子型光引发剂可选自如下结构：
Figure PCTCN2017095371-appb-000004
Figure PCTCN2017095371-appb-000005
Figure PCTCN2017095371-appb-000006
Figure PCTCN2017095371-appb-000007
Figure PCTCN2017095371-appb-000008
Figure PCTCN2017095371-appb-000009
Figure PCTCN2017095371-appb-000010
Figure PCTCN2017095371-appb-000011
Figure PCTCN2017095371-appb-000012
本发明还涉及上述通式(I)所示的新型阳离子型光引发剂的制备方法，反应流程如下所示：
Figure PCTCN2017095371-appb-000013
其中，当R3代表S+(R6)(R7)基团时，R3 ’表示氢，其余情况下R3 ’＝R3；
具体包括下列步骤：
(1)中间体的合成
原料a和原料b在三氯化铝或氯化锌作用下于有机溶剂中发生傅克反应，合成中间体；
(2)产物的合成
将中间体加入溶解有NaX或KX的有机溶剂中，搅拌至溶解，随后加入去离子水搅拌，析出固体，抽滤、重结晶，得到产物；其中，NaX和KX的X即为上述非亲核性阴离子。
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。其中，原料a可参照例如中国专利申请号为201010557275.7、200910030326.8、2015109373280.0等专利中公开的方法合成，在此将其全文引入以作为参考。
步骤(1)和(2)中涉及的反应是本领域合成类似化合物的常规反应。在知晓了本发明公开的合成思路的基础上，具体反应条件对本领域技术人员而言是容易确定的。
步骤(1)的傅克反应中，反应温度通常为-10-30℃。对使用的有机溶剂并没有特别限定，只要能够溶解原料且对反应无不良影响即可，如二氯甲烷、二氯乙烷、苯、甲苯、二甲苯等。
步骤(2)的离子交换反应是在溶剂体系中进行，使用的有机溶剂并没有特别限定，只要能够溶解反应原料、能与水互溶且对反应无不良影响即可，如丙酮、甲乙酮、甲基异丁基酮、环己酮、甲醇、乙醇、异丙醇。反应温度没有特别的限定，室温即可。
本发明还包括上述通式(I)所示的阳离子型光引发剂在光固化组合物的应用。所述阳离子型光引发剂或其混合物可以直接在配方中使用，也可与其他阳离子型光引发剂配合使用。在使用中，含有本发明所述阳离子型光引发剂的光固化组合物还可根据需要任选地添加公知的添加剂，如溶剂、增感剂、颜料、填充剂、消泡剂、流平剂及非反应性树脂等。非限制性地，本发明的光引发剂可应用在涂料、涂布剂、光致抗蚀剂、光敏材料、密封材料、油墨、粘合剂、偏光膜、环氧地坪等方面。该光引发剂在应用过程中能够匹配更长的吸收波长，能带来优异的溶解性、低迁移性和耐黄变性能。
具体实施方式
以下将结合具体实施例对本发明作进一步说明，但不应将其理解为对本发明保护范围的限制。
制备实施例
实施例1
Figure PCTCN2017095371-appb-000014
(1)中间体1a的制备
向1000mL的四口烧瓶中加入83g原料1a、三氯化铝67g、二氯甲烷200mL，冰水浴降至0℃。将101g原料1b溶解于200mL二氯甲烷中，形成混合溶液。随后将混合溶液装入滴液漏斗，控温10℃以下，向四口烧瓶中滴加该混合溶液，约2h滴加完。滴加完继续搅拌24h，液相跟踪至原料浓度不再发生变化，接着将物料缓慢倒入800g去离子水中，搅拌，固体析出，抽滤得淡黄色固体。将该淡黄色固体在80℃烘箱干燥2h，得152g中间体1a，收率79％，纯度98％。
(2)化合物1的制备
将152g六氟磷酸钾溶解于150mL丙酮中，然后加入步骤(1)制备的中间体1a 115g，常温搅拌至中间体1a溶解，接着加入300mL去离子水，白色固体析出，抽滤，甲醇重结晶得196g固体，70℃烘5h，得化合物1，收率92％，纯度98％。
产物结构通过MS和1H-NMR得到确认。
MS(m/z):352(M+1)+；
1H-NMR(CDCl3，500MHz)：3.9013(2H，s)，7.3611-7.7658(18H，m)。
实施例2
Figure PCTCN2017095371-appb-000015
(1)中间体2a的制备
向500mL的四口烧瓶中加入40g原料2a、三氯化铝14g、二氯甲烷50mL，冰水浴降至0℃。将31g原料2b溶解于50mL二氯甲烷中，形成混合溶液。随后将混合溶液装入滴液漏斗，控温10℃以下，向四口烧瓶中滴加该混合溶液，约2h滴加完，滴加完继续搅拌24h，液相跟踪至原料浓度不再发生变化，接着将物料缓慢倒入200g去离子水中，搅拌，固体析出，抽滤得淡黄色固体。将该淡黄色固体在80℃烘箱干燥2h，得46g中间体2a，收率64％，纯度98％。
(2)化合物2的制备
将45g四(五氟苯基)硼酸钠溶解于100mL丙酮中，然后加入步骤(1)制备的中间体2a 43g，常温搅拌至中间体2a溶解，接着加入200mL去离子水，白色固体析出，抽滤，甲醇重结晶得76g固体，70℃烘5h，得化合物2，收率90％，纯度98％。
MS(m/z):687(M+1)+；
1H-NMR(CDCl3，500MHz)：0.9642(6H，t)，1.1332-1.1932(4H，m)，1.2911-1.3027(4H，m)，1.8694-1.8663(4H,m)，2.3433(3H，s)，7.3281-8.1477(24H，m)。
实施例3
Figure PCTCN2017095371-appb-000016
(1)中间体3a的制备
向500mL的四口烧瓶中加入22g原料3a、三氯化铝28g、二氯甲烷50mL，冰水浴降至0℃。将46g原料3b溶解于100mL二氯甲烷中，形成混合溶液。随后将混合溶液装入滴液漏斗，控温10℃以下，向四口烧瓶中滴加该混合溶液，约2h滴加完，滴加完继续搅拌24h，液相跟踪至原料不再发生变化，接着将物料缓慢倒入200g去离子水中，搅拌，固体析出，抽滤得淡黄色固体。将该淡黄色固体在80℃烘箱干燥2h，得56g中间体3a，收率65％，纯度98％。
(2)化合物3的制备
将60g全氟丁基磺酸钠溶解于100mL丙酮中，然后加入步骤(1)制备的中间体3a 55g，常温搅拌至中间体3a溶解，接着加入200mL去离子水，白色固体析出，抽滤，甲醇重结晶得88g固体，70℃烘5h，得化合物3，收率90％，纯度98％。
MS(m/z):650(M+1)+；
1H-NMR(CDCl3，500MHz)：0.9444-0.9601(6H，t)，1.9086-1.9146(4H,m)，2.3607(12H，s)，7.1061-7.7677(22H，m)。
实施例4-18
参照实施例1-3的方法，利用相应原料合成了如下表1中所示的化合物4-18。目标产物的结构及其质谱数据列于表1。
表1
Figure PCTCN2017095371-appb-000017
Figure PCTCN2017095371-appb-000018
Figure PCTCN2017095371-appb-000019
Figure PCTCN2017095371-appb-000020
Figure PCTCN2017095371-appb-000021
性能评价
通过配制示例性光固化组合物，对本发明式(I)所示光引发剂的各项应用性能进行评价，包括感光性能、储存稳定性、迁移性、耐黄变等方面。
1.光固化组合物配制
按照表2所示配方，配制光固化组合物。首先将阳离子型光引发剂溶解在溶剂碳酸丙烯酯中，然后与阳离子聚合性单体混合均匀，配制得到光固化组合物。
其中，所述阳离子聚合性单体是A1、A2和A3中的一种或两种以上的组合：
A1：3,4-环氧环己基甲酸-3’,4’-环氧环己基甲酯(CAS：2386-87-0)；
A2：已二酸双(3,4-环氧环己基甲酯)(CAS:3130-19-6)；
A3：1,4-环己烷二甲醇二乙烯基醚(CAS:17351-75-6)。
所述阳离子型光引发剂是本发明的阳离子型光引发剂或者作为对比的化合物A和/或B。
化合物A：
Figure PCTCN2017095371-appb-000022
化合物B：
Figure PCTCN2017095371-appb-000023
表2中各组分的用量均为质量份。
表2
Figure PCTCN2017095371-appb-000024
2.感光性能测试
将上述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，用高压汞灯(曝光机型号RW-UV70201，波长200-500nm，光强100mW/cm2)照射对涂膜进行曝光，曝光时间2s，室温放置2min，观察其固化膜的铅笔硬度(测试方法参照GB/T 6739-1986)；铅笔硬度越高，则表示组合物的光固化性越良好，即引发剂的感度越优异)。
按照以下标准进行评价：
◎：铅笔硬度为2H以上；
○：铅笔硬度为H-2B；
●：铅笔硬度为2B以下或无法测定其铅笔硬度。
3.迁移性评价
将上述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，用高压汞灯(曝光机型号RW-UV70201，波长200-500nm，光强100mW/cm2)照射对涂膜进行曝光，曝光时间4s，得到所需的固化膜。接着，以10mL甲醇为模拟液，将固化后的膜放于模拟液中，室温放置24h，用HPLC分析析出光引发剂的量(岛津LC-MS2020，流动相甲醇/水＝55/45，0.5％磷酸二氢盐)，以液相中出峰的百分含量进行比较，液相中相对引发剂含量越低，越不易迁移。
按照以下标准进行评价：
◎：未检测出引发剂；
●：检测出引发剂；
4.耐黄变性评价
将上述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，用高压汞灯(曝光机型号RW-UV70201，波长200-500nm，光强100mW/cm2)照射对涂膜进行曝光，曝光时间4s，得到所需的固化膜。
接着，采用RW-UV.2BP紫外老化试验箱进行老化实验，光源为高压汞灯(主波长365nm，整机功率：约2.2KW)，连续照射固化膜6h，观察固化膜的黄变情况：
◎：无色透明，表面光滑；
○：微黄或表面有发粘；
●：表面发黄或粘度增大。
5.储存稳定性
将上述所得的光固化组合物在遮光下在80℃烘箱内进行加热24h，避光常温保存1个月，测量其加热前及放置1个月后组合物的粘度。粘度越不上升，则表示储存稳定性越好。
按照以下标准进行评价：
◎：粘度变化小于1.5倍；
○：粘度变化为1.5倍以上。
评价结果见表3。
表3
实施例/比较例 感光性 迁移性 耐黄变性 储存稳定性
实施例19 ◎ ◎ ◎ ◎
实施例20 ◎ ◎ ◎ ◎
实施例21 ◎ ◎ ◎ ◎
实施例22 ◎ ◎ ◎ ◎
实施例23 ◎ ◎ ◎ ◎
实施例24 ◎ ◎ ◎ ◎
实施例25 ◎ ◎ ◎ ◎
实施例26 ◎ ◎ ◎ ◎
实施例27 ◎ ◎ ◎ ◎
实施例28 ◎ ◎ ◎ ◎
实施例29 ◎ ◎ ◎ ◎
比较例1 ● ○ ● ○
比较例2 ● ○ ● ○
比较例3 ○ ○ ○ ○
比较例4 ○ ○ ○ ○
比较例5 ○ ○ ○ ○
从表3的结果可以看出，相比于常规的硫鎓盐光引发剂(化合物A和B)，使用本发明阳离子型光引发剂的光固化组合物感光性能优异，固化膜的铅笔硬度均超过2H，且具有不易迁移、耐黄变、储存稳定性更优的特点。
需要注意的是，实施例19-29中使用的阳离子型光引发剂的分子量比化合物A或B都大，在同等质量下摩尔量相对较低，而其铅笔硬度均在2H以上，更进一步说明本发明的光引发剂在感光性能方面的优势。

Claims (13)

  1. 一种阳离子型光引发剂，其特征在于，所述阳离子型光引发剂具有如通式(I)所示的结构：
    Figure PCTCN2017095371-appb-100001
    其中，
    R1和R2相互独立地表示卤素、OH、CN、NO2、C1-C20的直链或支链烷基、C3-C20的环烷基、C4-C20的环烷基烷基、C4-C20的烷基环烷基、C6-C40的芳基或杂芳基，其中的-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代；
    m1和m2分别表示R1和R2的个数，m1和m2相互独立地取0-3的整数；
    R4和R5相互独立地表示氢、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C12的环烷基烷基、C4-C12的烷基环烷基，其中的-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代；并且任选地，R4和R5可链接成环；
    R6和R7可相同，也可不同，两者相互独立地表示苯基、二苯硫醚基、二苯甲酮基、芴基、二苯醚基、咔唑基，其中的氢可任选地被卤素、CN、NO2、或C1-C8的烷基所取代，且所述C1-C8的烷基中的-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代；任选地，R6和R7可连接成环；
    R3代表氢、卤素、CN、NO2、R8、-CO-R8或S+(R6)(R7)基团；R8表示C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C15的环烷基烷基、C6-C20的芳基、C7-C20的芳基烷基，其中，环烷基结构和芳基结构中的H可任选地被C1-C6的烷基所取代，-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代；
    X-表示非亲核性阴离子；
    n为1或2。
  2. 根据权利要求1所述的阳离子型光引发剂，其特征在于：R1和R2相互独立地表示卤素、OH、CN、NO2、C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C12的环烷基烷基、C4-C12的烷基环烷基、C6-C20的芳基或杂芳基，其中的-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代。
  3. 根据权利要求1或2所述的阳离子型光引发剂，其特征在于：m1和m2相互独立地取0-2的整数，优选地，m1和m2均为0。
  4. 根据权利要求1所述的阳离子型光引发剂，其特征在于：R4和R5相互独立地表示氢、C1-C8的直链或支链烷基、C3-C6的环烷基、C4-C10的环烷基烷基，其中的非环-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代；并且任选地，R3和R4可彼此相连以形成环烷基。
  5. 根据权利要求1所述的阳离子型光引发剂，其特征在于：R6和R7相互独立地表示苯基、二苯硫醚基、二苯甲酮基、芴基、二苯醚基、咔唑基，其中的氢可任选地被CN、NO2、或C1-C4的烷基所取代，且所述C1-C4的烷基中的-CH2-可任选地被-O-、-S-、-CO-、-COO-或-OCO-所取代。
  6. 根据权利要求1所述的阳离子型光引发剂，其特征在于，R6和R7彼此相连，通过硫离子成环，形成下列基团的一种：
    Figure PCTCN2017095371-appb-100002
  7. 根据权利要求1所述的阳离子型光引发剂，其特征在于：R3代表氢、卤素、CN、NO2、R8、-CO-R8或S+(R6)(R7)基团；R8表示C1-C6的直链或支链烷基、C3-C8的环烷基、C4-C10的环烷基烷基、C6-C10的芳基、C7-C12的芳基烷基，其中，环烷基结构和芳基结构中的H可任选地被C1-C4的烷基所取代，非环-CH2-可任选地被-O-、-S-、-NH-、-CO-、-COO-或-OCO-所取代。
  8. 根据权利要求1或7所述的阳离子型光引发剂，其特征在于：当R3表示S+(R6)(R7)基团时，R3与另一侧的S+(R6)(R7)基团左右对称。
  9. 根据权利要求1所述的阳离子型光引发剂，其特征在于：X-选自CmF2m+1SO3 -、BF4 -、SbF6 -、AsF6 -、PF6 -或B(C6Q5)4 -，其中Q代表氢或卤素，m为1-8的整数。
  10. 根据权利要求1所述的阳离子型光引发剂，其特征在于：n的取值与通式(I)中S+(R6)(R7)基团的数量相同。
  11. 权利要求1-10中任一项所述的阳离子型光引发剂的制备方法，其特征在于，采用的反应流程如下所示：
    Figure PCTCN2017095371-appb-100003
    其中，当R3代表S+(R6)(R7)基团时，R3’表示氢，其余情况下R3’＝R3；
    所述制备方法具体包括下列步骤：
    (1)中间体的合成
    原料a和原料b在三氯化铝或氯化锌作用下于有机溶剂中发生傅克反应，合成中间体；
    (2)产物的合成
    将所述中间体加入溶解有NaX或KX的有机溶剂中，搅拌至溶解，随后加入去离子水搅拌，析出固体，抽滤、重结晶，得到产物；所述NaX和所述KX中的X表示非亲核性阴离子。
  12. 权利要求1-10中任一项所述的阳离子型光引发剂在光固化组合物的应用。
  13. 根据权利要求12所述的应用，其特征在于：所述的阳离子型光引发剂用于制作涂料、涂布剂、光致抗蚀剂、光敏材料、密封材料、油墨、粘合剂、偏光膜、环氧地坪。
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