WO2020200019A1 - Habi类混合光引发剂在uvled光固化中的应用 - Google Patents

Habi类混合光引发剂在uvled光固化中的应用 Download PDF

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WO2020200019A1
WO2020200019A1 PCT/CN2020/081292 CN2020081292W WO2020200019A1 WO 2020200019 A1 WO2020200019 A1 WO 2020200019A1 CN 2020081292 W CN2020081292 W CN 2020081292W WO 2020200019 A1 WO2020200019 A1 WO 2020200019A1
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meth
bis
habi
application according
compounds
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PCT/CN2020/081292
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French (fr)
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钱彬
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常州格林感光新材料有限公司
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Priority to KR1020217035062A priority Critical patent/KR102648080B1/ko
Priority to JP2021557999A priority patent/JP7223456B2/ja
Publication of WO2020200019A1 publication Critical patent/WO2020200019A1/zh

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

Definitions

  • the invention belongs to the technical field of organic chemistry and light curing, and specifically relates to the application of HABI-type mixed photoinitiators in UVLED light curing.
  • UVLED technology is gradually replacing the traditional high-pressure mercury lamp technology.
  • UVLED has many advantages, such as long service life, low energy consumption, cold light source, no mercury, stable light output, wide applicability, and almost zero maintenance cost.
  • the most commonly used UVLED light source has a wavelength between 355-420nm. As a photoinitiator suitable for UVLED technology, it needs to have absorption in this wavelength region. At the same time, since UVLED applications usually require high concentrations of photoactive substances, the photoinitiator is also required to have good compatibility with other components in the photocuring system Sex. At present, thioxanthone (such as isopropyl thioxanthone ITX) and its derivatives, and acyl phosphine oxide are the most commonly used photoinitiators in this field. However, as a single-wavelength UVLED light source, high-sensitivity photoinitiators, such as ITX, TPO, etc., that match the wavelength are usually selected.
  • ITX isopropyl thioxanthone ITX
  • TPO acyl phosphine oxide
  • the bisimidazole photoinitiator is formed by the coupling of two monoimidazoles. Under the condition of light or heating, the chemical bond connecting the two imidazole groups will be broken to generate monoimidazole radicals, which can be opposed to macromolecular radicals. The stable existence is not easily quenched by oxygen, and it is suitable for printing plate making, photosensitive imaging, printed circuit board and other fields. Bisimidazole photoinitiators can effectively solve the problems of surface dryness, odor and yellowing during use. However, due to the problems of solvent, poor sensitivity or difficulty in taking care of both at the same time, bisimidazole photoinitiators are used as the main initiator. The application in the field of UVLED light curing has not been reported yet. How to apply the bisimidazole photoinitiator to the formula system using LED as the light source to solve the problems of surface dryness, odor and yellowing existing in ITX and TPO has become an important research direction in this field.
  • the purpose of the present invention is to provide an application of hexaarylbisimidazole (HABI) mixed photoinitiator in UVLED light curing.
  • HABI hexaarylbisimidazole
  • the photosensitive resin composition containing a specific HABI-type mixed photoinitiator has excellent comprehensive performance under LED light source, good compatibility and high sensitivity, can replace traditional TPO and ITX initiators, solve its surface dry problem, and has no Odor and low yellowing characteristics.
  • the photosensitive resin composition used includes the following components:
  • HABI-type mixed photoinitiator which has a structure as shown in general formula (I), which contains 2-1', 2-3', 2'-1 and 2'-3
  • the bisimidazole compound at the connection position, and the total mass percentage of the four bisimidazole compounds at the connection position in the HABI mixed photoinitiator is more than 92%
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group;
  • At least one ortho-position substituent on the 2-position or 2'-position aryl group is an electron withdrawing substituent, the 4-position aryl group or the 4'-position aryl group or the 5-position aryl group or the 5'-position At least one substituent on the aryl group has an electron-donating substituent;
  • the molar extinction coefficient of the HABI-type mixed photoinitiator at 355-420nm is greater than 6000 and less than 13000;
  • the HABI-based mixed photoinitiator and other components form a photosensitive resin composition, which is used in the form of a composition.
  • the HABI-type mixed photoinitiator of the present invention has a structure as shown in the general formula (I), which contains bisimidazole compounds with four connection positions of 2-1', 2-3', 2'-1 and 2'-3 , And the total mass percentage of the four bisimidazole compounds in the mixed photoinitiator is above 92%,
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 may be the same or different, and each independently represents a substituted or unsubstituted aryl group.
  • the electron-withdrawing substituents on the aryl group are selected from halogen, nitro, cyano, and amine groups, and the electron-donating substituents on the aryl group are selected from methoxy and C 3 -C 10 branched chains.
  • the bisimidazole compounds satisfying the four connection positions 2-1', 2-3', 2'-1 and 2'-3 of the structure represented by the general formula (I) are specifically the following structures:
  • the aryl group is preferably a phenyl group.
  • the substituted aryl group may be mono-substituted or poly-substituted.
  • the substituents on the aryl group can be halogen, nitro, cyano, amino, hydroxyl, C 1 -C 20 alkyl or alkenyl, C 1 -C 8 alkoxy, wherein each independently
  • the methylene group in the variable ie, each substituent may be optionally substituted with oxygen, sulfur, or imino groups.
  • the substituent on the aryl group can be fluorine, chlorine, bromine, nitro, cyano, amino, hydroxyl, C 1 -C 10 alkyl or alkenyl, C 1 -C 5 alkoxy Group, wherein the methylene group in each independent variable can be optionally substituted with oxygen, sulfur, or imino groups.
  • At least one of Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , and Ar 6 is an aryl group containing a halogen substituent.
  • the halogen substituent is chlorine.
  • the HABI-type mixed photoinitiator mentioned in this application is formed by coupling two triarylimidazoles (which can be the same or different, depending on the substituents on the aryl group). Due to the inductive effect of the substituents on the benzene ring, the ⁇ electron cloud density of the benzene ring is reduced. The inductive effect promotes the distortion of the benzene ring, and the conjugate center on the imidazole ring is shifted, making the substituted phenyl and imidazole not in the same plane ( The three aryl imidazoles form a curved state). When the two imidazoles are finally coupled, the connection of N and C presents different spatial configurations, which greatly affects the performance of HABI.
  • HABI compounds such as the general formula (I) may also There are 1-4', 1-5', 3-4', 3-5', 1-1', 1-3', 3-1', 3-3', 4-1', 4-3' , 5-1', 5-3' and other connection positions.
  • the applicant’s research found that only when the four linking sites 2-1', 2-3', 2'-1, and 2'-3 exist and the total content accounts for more than 92% of the total amount of HABI, HABI can show the best performance. Excellent solubility and sensitivity.
  • the solubility of a single substance of any kind of linking site is far less than the above-mentioned mixed photoinitiator, and if the total content of these four linking sites is less than 92%, the sensitivity will obviously become lower.
  • CN1292892A mentioned a HABI photoinitiator used in photoresist photopolymerization systems, namely 2,2',5-tris(o-chlorophenyl)-4-( 3,4-Dimethoxyphenyl)-4',5'-diphenyl-1,2-diimidazole, commonly referred to as "TCDM-HABI", the document mentions that the use of at least one affinity HABI with water substituents (such as methoxy) can greatly reduce the amount of sludge in the recycled developer.
  • TCDM-HABI 2,2',5-tris(o-chlorophenyl)-4-( 3,4-Dimethoxyphenyl)-4',5'-diphenyl-1,2-diimidazole
  • the bisimidazoles satisfying the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 of the general formula (I) are preferred.
  • the total mass percentage of the compound in it is more than 95%, and it is particularly preferred to have four connection positions 2-1', 2-3', 2'-1 and 2'-3 satisfying the structure represented by the general formula (I) Composition of bisimidazole compound.
  • HABI photoinitiators are well-known photoinitiators in the photoresist field. They can be prepared by oxidative coupling of triarylimidazoles or substituted triarylimidazoles. The specific preparation process can be referred to, for example, US3784557, US4622286 and US4311783. There are technical records (the full text is hereby incorporated as a reference). On the basis of the existing process, adding a solvent recrystallization process can easily obtain the HABI-type mixed photoinitiator meeting the above composition requirements of the present invention.
  • the solvent may be one or a combination of two or more of toluene, methanol, ethyl acetate, dichloromethane, and water.
  • the preparation of the HABI-type hybrid photoinitiator can also refer to the content recorded in the applicant's previous application (application number CN201811451262.4), which is hereby incorporated in its entirety for reference.
  • the photo-initiated activity of HABI compounds is affected by the electronic and stereo effects of the substituents on the aromatic ring.
  • at least one ortho-substituent on the 2-position or 2'-position aryl group in the triarylimidazole or substituted triarylimidazole compound used in the synthesis of the HABI-type hybrid photoinitiator of the present invention is adsorbed.
  • Electron substituents, at least one substituent on the 4-position aryl group, 4'-position aryl group, 5-position aryl group, or 5'-position aryl group has an electron-donating substituent.
  • the HABI-based mixed photoinitiator has a molar extinction coefficient greater than 6000 and less than 13000 at 355-420 nm.
  • the molar extinction coefficient of the initiator is less than 6000, the absorbance of the initiator is insufficient, and the curing speed of the composition becomes slow; if the molar extinction coefficient of the initiator is greater than 13000, the surface layer is cured too fast, and the deep layer curing is insufficient to cause pattern defects.
  • the main product is a mixture of the hydrogen-containing N on one imidazole and the 2-position C on the other imidazole.
  • the monoimidazole has an asymmetric structure, such as TCTM as follows, the structure of the product obtained by coupling itself has the same structure of 2'-1 and 2-1', 2'-3 and 2-3 The structure of 'is also the same, so its main structure is the product of 2'-1 and 2-3'.
  • the main product structure is 2-1', 2-3', Two bisimidazole compounds with 2'-1 and 2'-3 connection positions.
  • the HABI-based hybrid photoinitiator of the present invention may be selected from or include at least one of the following combinations:
  • the photosensitive resin composition containing the above-mentioned HABI-type mixed photoinitiator has high photosensitivity in the wavelength range of 355-420nm, so that it can adapt to existing LED light sources of different wavelengths, such as 365nm, 385nm , 395nm, 405nm, making the photocurable composition suitable for many types of optical imaging equipment.
  • the content of the HABI-based mixed photoinitiator is 0.1-20 parts by weight, preferably 1-15 parts by weight, more preferably 2-10 parts by weight. Within this content range, the composition can exhibit good system compatibility and excellent curing performance.
  • the compound having an ethylenically unsaturated double bond can promote the formation of a film of the photosensitive resin composition.
  • the compound having an ethylenically unsaturated double bond is not particularly limited, as long as a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used.
  • examples include: compounds obtained by reacting ⁇ , ⁇ -unsaturated carboxylic acids with polyhydric alcohols, bisphenol A (meth)acrylate compounds, ⁇ , ⁇ -unsaturated carboxylic acids, and glycidyl-containing compounds
  • urethane monomers such as (meth)acrylate compounds with urethane bonds in the molecule, nonylphenoxy polyvinyloxy acrylate, ⁇ -chloro- ⁇ -hydroxypropyl - ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxyethyl- ⁇ '-(meth)acryloyloxyethyl-phthalate, ⁇ -hydroxypropyl- ⁇ '-(meth)
  • Examples of the compound obtained by reacting the above-mentioned ⁇ , ⁇ -unsaturated carboxylic acid with a polyhydric alcohol include polyethylene glycol di(meth)acrylate having an ethylene number of 2-14, and a propylene number of 2 Polypropylene glycol di(meth)acrylate of 14, ethylene number of 2-14 and propylene number of 2-14 polyethylene ⁇ polypropylene glycol di(meth)acrylate, trimethylol Propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO modified trimethylolpropane tri(meth)acrylate Base) acrylate, EO, PO modified trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, two Pentaerythritol penta
  • EO means ethylene oxide
  • PO means propylene oxide
  • a PO-modified compound means a compound having a block structure of an oxypropylene group.
  • Examples of the bisphenol A-based (meth)acrylate compound include: 2,2-bis ⁇ 4-[(meth)acryloxypolyethoxy]phenyl ⁇ propane, 2,2- Bis ⁇ 4-[(meth)acryloxypolypropoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxypolybutoxy]phenyl ⁇ propane, 2,2-Bis ⁇ 4-[(meth)acryloyloxypolyethoxypolypropoxy]phenyl ⁇ propane and the like.
  • 2,2-bis ⁇ 4-[(meth)acryloyloxypolyethoxy]phenyl ⁇ propane there may be mentioned: 2,2-bis ⁇ 4-[(meth)acryloyloxy Diethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxytriethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(methyl )Acryloyloxytetraethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloxypentaethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4- [(Meth)acryloyloxyhexaethoxy]phenyl ⁇ propane, 2,2-bis ⁇ 4-[(meth)acryloyloxyheptethoxy]phenyl ⁇ propane, 2,2- Bis ⁇ 4-[(meth)acryloyloxyoctaethoxy]phenyl ⁇ propane, 2,2-bis ⁇
  • the number of oxyethylene groups in one molecule of the 2,2-bis ⁇ 4-[(meth)acryloyloxypolyethoxy]phenyl ⁇ propane is preferably 4-20, and more preferably 8-15. These compounds may be used alone or in combination of two or more kinds.
  • the (meth)acrylate compound having a urethane bond in the molecule a (meth)acrylic monomer having an OH group at the ⁇ -position and a diisocyanate compound (isophorone diisocyanate, 2 ,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, etc.) addition reaction product, tris((meth)acryloyloxytetraethylene glycol isocyanate) ] Hexamethylene isocyanurate, EO modified urethane di(meth)acrylate, PO modified urethane di(meth)acrylate, EO, PO modified urethane di(meth)acrylic acid Ester etc. These compounds may be used alone or in combination of two or more kinds.
  • nonylphenoxy polyvinyloxy acrylate nonylphenoxy tetravinyloxy acrylate, nonylphenoxy pentavinyloxy acrylate, nonylphenoxy hexaethylene Oxyacrylate, nonylphenoxy heptavinyloxy acrylate, nonylphenoxy octavinyloxy acrylate, nonylphenoxy nonavinyloxy acrylate, nonylphenoxydecaethyleneoxy Acrylate, nonylphenoxyundecenyloxy acrylate, etc. These compounds may be used alone or in combination of two or more kinds.
  • phthalic acid compound examples include: ⁇ -chloro- ⁇ -hydroxypropyl- ⁇ '-(meth)acryloyloxyethyl phthalate, ⁇ -hydroxyalkyl- ⁇ '-(Meth)acryloyloxyalkyl phthalate, etc. These compounds may be used alone or in combination of two or more kinds.
  • the alkyl (meth)acrylate may, for example, be methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, N-Butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenyl (meth)acrylate, (methyl) ) Isobornyl acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-hydroxypropyl ester, benzyl (meth)acrylate, amyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isooctyl (meth)
  • These compounds may be used alone or in combination of two or more kinds.
  • the compound having an ethylenically unsaturated double bond is preferably a bisphenol A-based (meth)acrylate compound and a (meth)acrylate compound having a urethane bond in the molecule. From the viewpoint of improving sensitivity and resolution, bisphenol A-based (meth)acrylate compounds are preferred.
  • the content of the compound having an ethylenically unsaturated double bond is 25-99 parts by weight, preferably 55-90 parts by weight.
  • the photosensitive resin composition of the present invention further includes a hydrogen donor.
  • the bisimidazole compounds are cleaved after exposure to light, and the monoimidazole radicals produced are larger in volume. The steric hindrance makes the activity less, and it is difficult to initiate monomer polymerization alone. If used in conjunction with hydrogen donors, the monoimidazole radicals are easy The active hydrogen on the hydrogen donor is taken away to generate new active free radicals, which in turn initiates monomer polymerization.
  • suitable hydrogen donors may be amines or amine-modified compounds, thiol-based compounds, which have available hydrogen connected to the carbon adjacent to the heteroatom. These compounds can be used alone or in combination of two or more of them.
  • the amine compound may be an aliphatic amine, a cycloaliphatic amine, an aromatic amine, an aromatic-aliphatic amine, a heterocyclic amine, an oligomeric amine, or a polymeric amine.
  • They can be primary, secondary or tertiary amines, such as butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, N-phenylglycine, tributylamine, Ethylamine, phenyl-diethanolamine, triethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, dimethylaminobenzoate, Michler'sketone (4,4'-di- Dimethylaminobenzophenone), and corresponding derivatives.
  • primary, secondary or tertiary amines such as butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, N-phenylglycine, tributylamine, Ethylamine, phenyl-diethanolamine, triethanolamine
  • Amine-modified compounds such as amine-modified acrylate compounds can be used as hydrogen donors.
  • Examples of such amine-modified acrylate compounds include acrylates modified by reaction with primary or secondary amines, such as those disclosed in US3,844,916, EP280222, US5,482,649 or US5,734,002, here The full text is incorporated as a reference.
  • preferred amines or amine-modified compounds are: EsacureA198 (bis-N,N-[4-dimethylaminobenzoyl)oxoethylene-1-yl]-methylamine) and EsacureEDB ( Ethyl-4-dimethylaminobenzoate) (both sold by Lamberti S.pA), 2-ethylhexyl-4-dimethylaminobenzoate and N-phenylglycine.
  • the thiol compound may be a primary thiol, a secondary thiol, and a multifunctional thiol, and a secondary thiol and a multifunctional thiol are preferred.
  • the thiol compound may be: 2-mercaptobenzothiazole (MBO), 2-mercaptobenzimidazole (MBI), dodecyl mercaptan, ethylene glycol bis(3-mercaptobutyrate) , 1,2-propanediol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3- Mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), dipentaerythritol hexa(3-mercapto
  • the content of the hydrogen donor is 0.01-15 parts by weight, preferably 0.1-15 parts by weight, more preferably 0.1-10 parts by weight, and the hydrogen donor is in accordance with the general formula (I
  • the weight ratio of the HABI-based mixed photoinitiator shown in) is preferably 1:20-1:3.
  • the photosensitive resin composition of the present invention may further contain other photoinitiators and/or sensitizers, so as to adjust the sensitivity of the photosensitive resin composition more flexibly through a common/synergistic effect.
  • the other photoinitiators and/or sensitizers may include (but are not limited to): bisimidazoles, pyrazolines, aromatic ketones, anthraquinones, benzoin and benzoin alkyl ethers, Oxime esters, triazines, triphenylamines, coumarins, thioxanthones, acridines and other photoinitiators known to those skilled in the art. These compounds may be used alone or in combination of two or more kinds.
  • bisimidazole compounds include: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole, 2,2',5-tris(ortho Chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2',5-tris(2-fluoro Phenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-diimidazole, 2,2'-bis(2,4-dichlorophenyl)-4 ,4',5,5'-tetraphenyl-diimidazole, 2,2'-bis(2-fluorophenyl)-4-(o-chlorophenyl)-5-(3,4-dimethoxy Phenyl)-4',5'-diphenyl-diimidazole, 2,2'
  • pyrazoline compounds include: 1-phenyl-3-(4-tert-butylstyryl)-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3 -Biphenyl-5-(4-tert-butylphenyl)pyrazoline, ethoxylated (9) trimethylol pyrazoline ester, ethoxylated (10) bisphenol A pyrazoline ester And its analogues.
  • These pyrazoline compounds may be used alone or in combination of two or more kinds.
  • the aromatic ketone compounds include: acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1 ,1-Dichloroacetophenone, benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4'-methyl diphenyl sulfide, 4-benzoyl-4'-ethyl Diphenyl sulfide, 4-benzoyl-4'-propyl diphenyl sulfide, 4,4'-bis(diethylamino)benzophenone, 4-p-toluene mercaptobenzophenone, 2 ,4,6-Trimethylbenzophenone, 4-methylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(methyl, ethyl Amino) benzophenone, acetophenone dimethyl ketal, benzil dimethyl ket
  • anthraquinone compounds include: 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2,3-dimethylanthraquinone, 2-ethylanthracene-9,10-diethyl, 1,2,3-trimethylanthracene-9,10-dioctyl, 2-ethylanthracene-9,10-bis(4-chlorobutyric acid Methyl ester), 2-(3-((3-ethyloxetan-3-yl)methoxy)-3-oxopropyl)anthracene-9,10-diethyl, 9,10 -Dibutoxyanthracene, 9,10-diethoxy-2-ethylanthracene, 9,10-bis(3-chloropropoxy)anthracene, 9,10-bis(2-hydroxyethylmer
  • benzoin and benzoin alkyl ether compounds include: benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether and the like. These benzoin and benzoin alkyl ether compounds may be used alone or in combination of two or more kinds.
  • the oxime ester compounds include: 1-(4-phenylthiophenyl)-n-octane-1,2-dione-2-benzoic acid oxime ester, 1-(6-(2-methyl Benzoyl)-9-ethylcarbazol-3-yl)-ethane-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazole- 3-yl)-butane-1-one-oxime acetate, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-propan-1-one-acetic acid Oxime ester, 1-(6-(2-methylbenzoyl)-9-ethylcarbazol-3-yl)-1-cyclohexyl-methane-1-one-acetoxime ester, 1-(6- (2-methylbenzoyl)-9-ethylcarbazol-3-yl)-3-cyclopenty
  • triazine compounds include: 2-(4-ethylbiphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-ethylene Methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 3- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazine -6-yl]phenylthio)propionic acid, 1,1,1,3,3,3-hexafluoroisopropyl-3- ⁇ 4-[2,4-bis(trichloromethyl)-s- Triazine-6-yl]phenylthio ⁇ propionate, ethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-yl]phenylthio ⁇ ethyl Ester, 2-ethoxyethyl-2- ⁇ 4-[2,4-bis(trichloromethyl)-s-triazin-6-y
  • the triphenylamine compound includes: N,N-bis-[4-(2-styryl-1-yl)-phenyl]-N,N-bis(2-ethyl-6methylbenzene) Yl)-1,1-bisphenyl-4,4-diamine, N,N-bis-[4-(2-styryl-1-yl)-4′-methylphenyl]-N, N-bis(2-ethyl-6methylphenyl)-1,1-bisphenyl-4,4-diamine and its analogs.
  • These triphenylamine compounds may be used alone or in combination of two or more kinds.
  • the coumarin compound includes: 3,3'-carbonyl bis(7-diethylamine coumarin), 3-benzoyl-7-diethylamine coumarin, 3,3'-carbonyl Bis(7-methoxycoumarin), 7-(diethylamino)-4-methylcoumarin, 3-(2-benzothiazole)-7-(diethylamino)coumarin , 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin), 3-benzoyl- 7-Methoxycoumarin and its analogues.
  • These coumarin compounds can be used alone or in combination of two or more kinds.
  • thioxanthone compounds include: thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2 -Chlorothioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diisopropylthioxanthone and the like. These thioxanthone compounds may be used alone or in combination of two or more kinds.
  • acridine compounds include: 9-phenyl acridine, 9-p-methylphenyl acridine, 9-m-methylphenyl acridine, 9-o-chlorophenyl acridine, 9-o-fluoro Phenyl acridine, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether cycloethane ether [4-(9-acridinyl)phenoxy]acetate (ie PAD107, Produced by Changzhou Qiangli Electronic New Materials Co., Ltd.), 1,7-bis(9-acridinyl)heptane, 9-ethylacridine, 9-(4-bromophenyl)acridine, 9-(3 -Chlorophenyl) acridine, 1,7-bis(9-acridine)heptane, 1,5-bis(9-acridinepentane), 1,3
  • the content of the other photoinitiator and/or sensitizer is not more than 8 parts by weight.
  • the photosensitive resin composition of the present invention may also contain appropriate amounts of other auxiliary agents as needed.
  • the auxiliary agent may include at least one of organic solvents, dyes, pigments, light developers, fillers, plasticizers, stabilizers, coating aids, peeling accelerators, and the like.
  • the organic solvent it is sufficient if it can dissolve the aforementioned components.
  • it may be glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, chlorine-containing solvents, etc., and coloring is particularly preferred. The choice is based on factors such as the solubility, coating properties, and safety of the alkali-soluble polymer.
  • the organic solvent may be ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), Methyl methoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene two Alcohol mono-tert-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy-2-propanol) ), propylene glycol monoethyl ether acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether), but
  • dyes, pigments and light developer can be: tris(4-dimethylaminophenyl)methane, tris(4-dimethylamino-2-methylphenyl)methane, fluoran dye , Toluenesulfonic acid monohydrate, basic fuchsin, phthalocyanine green and phthalocyanine blue and other phthalocyanine series, auramine base, para-fuchsin, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green , Diamond Green, Basic Blue 20, Brilliant Green, Eosin, Ethyl Violet, Erythrosine Sodium B, Methyl Green, Phenolphthalein, Alizarin Red S, Thymolphthalein, Methyl Violet 2B, Quinidine Red , Rose Bengal Sodium Agar, Mitanil Yellow, Thymol Sulfophthalein, Xylenol Blue, Methyl Orange, Orange IV, Diphenyl Flow Carbach
  • fillers such as silica, alumina, talc, calcium carbonate, and barium sulfate (not including the above-mentioned inorganic pigments).
  • the filler can be used alone or in a mixture of two or more.
  • phthalic acid such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, diallyl phthalate, etc.
  • Ester glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide, n-butylbenzenesulfonamide, triphenyl phosphate, triphenyl Methyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, tolyl diphenyl phosphate, tricresyl phosphate, 2-naphthyl phosphate Phenyl phosphate, tolyl di-2,6-xylyl phosphate, aromatic condensed phosphate, tris(chloropropyl esters, glycol
  • a stabilizer for example, it can be: hydroquinone, 1,4,4-trimethyl-diazobicyclo(3.2.2)-non-2-ene-2,3-dioxide, 1- Phenyl-3-pyrazolidinone, p-methoxyphenol, alkyl and aryl substituted hydroquinone and quinone, tert-butylcatechol, 1,2,3-benzenetriol, copper resinate, naphthylamine , ⁇ -naphthol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluoquinone and chloranil.
  • the stabilizer can be used singly or in combination of two or more.
  • a coating aid considering safety and versatility, it can be: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, Ethyl lactate, cyclohexanone, ⁇ -butyrolactone, dichloromethane, etc.
  • the coating aids can be used alone or in combination of two or more.
  • peeling accelerator exemplarily, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, phenolsulfonic acid, methyl, propyl, heptyl, octyl, decyl, dodecyl Alkylbenzene sulfonic acid and so on.
  • the peeling accelerator may be used alone or in combination of two or more.
  • the total content of the auxiliary agent does not exceed 10 parts by weight.
  • the wavelength of the LED light source is in the range of 355-420nm, which can be 365nm, 385nm, 395nm, 405nm, etc.
  • the above-mentioned photosensitive resin composition of the present invention can be used as an ink and coating composition for coating metal surfaces, wood surfaces, paper surfaces, plastic surfaces, and the like.
  • flexographic printing, offset printing, gravure printing or inkjet printing methods can be used to coat the ink or coating composition, and then be cured by radiation.
  • the aforementioned photosensitive resin composition of the present invention can be cured in the presence of oxygen, thereby eliminating the need to provide an inert oxygen-free environment during curing to prevent oxygen inhibition.
  • Figure 1 is a high performance liquid chromatogram of product A1.
  • Figure 2 is the structure spectrum obtained by single crystal diffraction of BCIM.
  • TAI 4-(4,5-Dimethoxyphenyl)-imidazole
  • Figure 1 is a high performance liquid chromatogram of product A1. The analysis results show that the total peak content of the four connection positions of 2-1', 2-3', 2'-1 and 2'-3 is 92.5%.
  • the product A1 is a mixture of two different monoimidazoles (ie INC, TAI) through self-coupling and mutual coupling, including BCIM, TCTM and TCDM.
  • BCIM monoimidazoles
  • TCTM TCTM
  • TCDM TCDM
  • BCIM has only one peak in the liquid phase, but two peak shapes are obtained by single crystal diffraction, see Figure 2. Combining the structural characteristics, it can be determined that the main product of the coupling of two monoimidazoles is a mixture of hydrogen-containing N on one imidazole and C on the 2 position of the other imidazole, which indicates that the structure of BCIM is the present invention.
  • the imidazole used to synthesize BCIM is INC, which is a symmetrical imidazole, so the 2'-1 and 2'-3 obtained by coupling are similar in polarity, and it is difficult to separate the liquid phase.
  • the structure of the product obtained by its own coupling has the same structure of 2'-1 and 2-1', and the structure of 2'-3 and 2-3' are also the same, so the main structure of BCIM is 2' -1 and 2'-3 two link products, the structural formulas are as follows, respectively BCIM1: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl- 1,2'-Diimidazole and BCIM2: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2',3-diimidazole;
  • TCTM is synthesized by asymmetric monoimidazole coupling. There are theoretically eight main structures connected by 1-2 and 2-3 link positions, but for self-coupled monoimidazole, the 2'-1 and 2-1' structures in the structure are the same , 2'-3 and 2-3' have the same structure, so for TCTM, there are actually four main structures connected by 1-2 and 2-3 connection positions.
  • TCTM1 2,2',5,5'-tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-2',3-diimidazole
  • TCTM2 2 ,2',4,5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole
  • TCTM3 2,2' ,5,5'-Tetra(o-chlorophenyl)-4,4'-bis(3,4-dimethoxyphenyl)-1,2'-diimidazole
  • TCTM4 2,2',4, 5'-Tetra(o-chlorophenyl)-4',5-bis(3,4-dimethoxyphenyl)-2',3-diimidazole, the structure is as follows:
  • TCDM is formed by the coupling of INC and TAI.
  • the main structure of the separated pure TCDM in the liquid phase is the product with four connection positions, and the LCMS confirms the structure of the product with the four connection positions.
  • Mass spectrometry analysis uses the software attached to the instrument to obtain molecular fragment peaks of 755 and 756.
  • the molecular weight of the product is 754, which is consistent with T+1 and T+2, which proves that the four products are similar in structure and have the same molecular weight.
  • TCDM is formed by two-by-two connection of symmetrical imidazole INC and asymmetrical imidazole TAI. There are four main structures connected at the 1-2 and 2-3 connection positions, and their compositions are:
  • TCDM1 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-diimidazole
  • TCDM2 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2',3-diimidazole
  • TCDM3 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-2,3'-diimidazole
  • TCDM4 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1',2-diimidazole
  • the product A1 is a combination of BCIM (BCIM1, BCIM2), TCTM (TCTM1, TCTM2, TCTM3, TCTM4) and TCDM (TCDM1, TCDM2, TCDM3, TCDM4), which consists of 2-1', 2
  • BCIM1, BCIM2 BCIM1
  • TCTM1, TCTM2, TCTM3, TCTM4 TCDM1, TCDM2, TCDM3, TCDM4
  • the test method of molar extinction coefficient is:
  • IR spectra acquired by Fourier transform infrared spectroscopy, and assigned to the acrylic double bond at 1408cm -1 and 810cm -1 peak area peak area before and after the light was measured using IR software.
  • the degree of reduction (%) of the peak area is calculated, thereby quantifying the degree of polymerization and further quantifying the efficiency of the photoinitiator.
  • the greater the reduction (%) of the peak area the higher the double bond conversion rate per unit time and the better the sensitivity of the initiator.
  • test results are shown in the following table, expressed as the reduction degree (%) of the peak area within 3S.
  • the above-mentioned HABI-type mixed photoinitiators (A1, A2, A3, and A3) of the present invention have a sensitivity similar to that of TPO and ITX.
  • the comparative examples (A4 and A) due to low solubility affect the In the formulation, although the solubility of the comparative examples (A6, A7, A8) is equivalent to that of the examples, the sensitivity is lower than that of the examples, and cannot achieve the effects of TPO and ITX; the comparative examples (A9, A10) are due to The substitution position does not comply with the substitution rule of the present invention, and the sensitivity is low under UVLED, and it is difficult to apply.
  • N-PG hydrogen donor 1 part by weight.
  • the sample of the composition to be tested was stirred evenly in the dark, sampled on the PET substrate, coated with 25# wire rod to form a coating film with a thickness of 25 ⁇ m, and then used an LED light source (radiation wavelength of 385nm, exposure 240mj/cm 2 ) The coating film is cured by radiation.
  • the curing of each formula is examined from two aspects: surface dryness and bottom dryness.
  • surface dryness Refer to the paint film drying time test standard GB/T 1728-1979 in the finger touch method to evaluate the surface curing, that is, lightly touch the coating with your fingers, and the surface is smooth, and the hands are not sticky to indicate that the surface is cured completely; the finger pull method is used to measure the bottom curing , That is, use your nails to gently pull the coating, and no peeling, no bottoming out indicates that the bottom layer is completely cured.
  • Yellowing test Use UVA (340) lamp as the light source, and place the exposed cured film test panel at a temperature of (120 ⁇ 5)°C, irradiance of 0.68W/m2, and dry (non-condensing) fluorescent ultraviolet In the aging machine, the whole process maintains continuous light for 168 hours. After the light is over, take it out and compare it with the test panel after the initial TPO exposure. Use a colorimeter to measure the color change. The color change value unit is ⁇ E*. The smaller the measured value, the closer the color.
  • the above-mentioned HABI-type mixed photoinitiator of the present invention has better surface drying effect, lower odor and lower yellowness, whether compared with A9 or the prior art TPO and ITX. Change, safer to use.

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Abstract

一种六芳基双咪唑类混合光引发剂在UVLED光固化中的应用。包含特定HABI类混合光引发剂的感光性树脂组合物在LED光源下综合性能优异，相容性好、感光度高，能够替代传统的TPO、ITX引发剂，解决其表干问题，且具有无气味、低黄变的特点。

Description

HABI类混合光引发剂在UVLED光固化中的应用 技术领域
本发明属于有机化学和光固化技术领域，具体涉及HABI类混合光引发剂在UVLED光固化中的应用。
背景技术
随着光固化技术的发展，UVLED技术正逐步取代传统的高压汞灯技术。UVLED具有诸多优点，诸如使用寿命长、能耗低、冷光源、不含汞、光输出稳定、适用性广、维护成本几乎为零等。
最常用的UVLED光源的波长在355-420nm之间。作为适用UVLED技术的光引发剂，需要在该波长区域内有吸收，同时鉴于UVLED应用通常需要高浓度的光活性物质，还要求光引发剂与光固化体系中的其它组分具有良好的相容性。目前，噻吨酮(如异丙基噻吨酮ITX)及其衍生物、与酰基氧化膦，是该领域最常用的光引发剂。然而，作为单一波长的UVLED光源，与其波长相匹配的通常选用高感度的光引发剂，如ITX、TPO等，这些引发剂光照后生成的自由基活性很高，极易被空气中的氧气所淬灭，所以开发适用于UVLED光源且不存在因氧阻聚导致的表干问题的引发剂成了该领域急需解决的问题。另外，噻吨酮类在曝光时趋于黄化，在成像例如喷墨打印中会因为这种不稳定的黄化性能而难以控制最终图像的色泽；酰基氧化膦引发剂使用时会生成中等挥发性醛类降解产物，产生不受欢迎的气味，大量使用会带来一些健康和安全问题。因此为了推动UVLED技术在光固化领域中的发展，亟需开发出具有改进性能的适用光引发剂，以满足UVLED 光源固化的要求。
双咪唑类光引发剂是由两个单咪唑耦合而成，在光照或加热情况下，连接两个咪唑基的化学键会发生断裂，生成单咪唑自由基，该自由基作为大分子自由基能相对稳定的存在不易被氧气所淬灭，适用于印刷制版、感光成像、印刷线路板等领域。双咪唑类光引发剂可以有效解决使用时产生的表干、气味、黄变等问题，但由于溶剂性、感度不佳或难以同时兼顾等问题，以双咪唑类光引发剂作为主引发剂在UVLED光固化领域中的应用还未有报导。如何将双咪唑类光引发剂应用到以LED为光源的配方体系中，从而解决现有ITX、TPO存在的表干、气味和黄变问题成为了本领域研究的重要方向。
发明内容
本发明的目的在于提供一种六芳基双咪唑(HABI)类混合光引发剂在UVLED光固化中的应用。包含特定HABI类混合光引发剂的感光性树脂组合物在LED光源下综合性能优异，相容性好、感光度高，能够替代传统的TPO、ITX引发剂，解决其表干问题，且具有无气味、低黄变的特点。
具体来说，HABI类混合光引发剂在UVLED光固化中的应用，其特征在于，使用的感光性树脂组合物包含下列组分：
(a)0.1-20重量份的HABI类混合光引发剂，具有如通式(I)所示结构，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，且该四种连接位的双咪唑化合物在HABI类混合光引发剂中的总质量百分含量为92％以上，
Figure PCTCN2020081292-appb-000001
其中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基；
并且其中，2-位或2’-位芳基上至少有一个邻位取代基为吸电子取代基，4-位芳基或4’-位芳基或5-位芳基或5’-位芳基上至少有一个取代基有供电子取代基；
所述HABI类混合光引发剂在355-420nm处摩尔消光系数大于6000且小于13000；
(b)25-99重量份的至少一种具有烯属不饱和双键的化合物；
(c)0.01-15重量份的供氢体，所述供氢体与通式(I)所示的HABI类混合光引发剂的重量比为1:20-1:1。
为更好的说明本发明的技术方案，下面对上述应用中的各部分(如感光性树脂组合物中的各组分等)分别进行阐述。
<感光性树脂组合物>
在本发明的UVLED光固化应用中，HABI类混合光引发剂与其它组分组成感光性树脂组合物，以组合物的形式使用。
HABI类混合光引发剂
本发明的HABI类混合光引发剂，具有如通式(I)所示结构，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，且该四种连接位的双咪 唑化合物在混合光引发剂中的总质量百分含量为92％以上，
Figure PCTCN2020081292-appb-000002
通式(I)中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基。
通式(I)中，芳基上的吸电子取代基选自卤素、硝基、氰基、胺基，芳基上的供电子取代基选自甲氧基、C 3-C 10的支链烷基或链烯基；
满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，具体为下列结构：
Figure PCTCN2020081292-appb-000003
通式(I)中，所述芳基优选是苯基。
所述取代的芳基可以是单取代的，也可以是多取代的。
优选地，芳基上的取代基可以为卤素、硝基、氰基、胺基、羟基、C 1-C 20的烷基或链烯基、C 1-C 8的烷氧基，其中各独立变量(即，各取代基)中的亚甲基可以任选地被氧、硫、亚胺基所取代。
更优选地，芳基上的取代基可以为氟、氯、溴、硝基、氰基、胺基、羟基、C 1-C 10的烷基或链烯基、C 1-C 5的烷氧基，其中各独立变量中的亚甲基可以任选地被氧、硫、亚胺基所取代。
进一步优选地，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6中至少一个是含有卤素取代基的芳基。特别优选地，卤素取代基为氯。
本申请中所说的HABI类混合光引发剂，由两个三芳基咪唑(可以相同也可以不同，取决于芳基上的取代基)偶合而成。由于苯环上取代基的诱导效应，降低了苯环的π电子云密度，诱导效应促使苯环扭曲，咪唑环上的共轭中心出现了偏移，使得取代苯基与咪唑不处于同一平面(三芳基咪唑成曲面态)，最终两个咪唑偶合时，N、C的连接呈现出不同的空间构型，从而对HABI的性能产生了极大影响。
除了上文所述的2-1’、2-3’、2’-1、2’-3四种连接位外，从结构上看，如通式(I)所示的HABI类化合物还可能存在1-4’、1-5’、3-4’、3-5’、1-1’、1-3’、3-1’、3-3’、4-1’、4-3’、5-1’、5-3’等连接位。然而申请人研究发现，只有当2-1’、2-3’、2’-1、2’-3四种连接位存在且总含量占HABI总量的92％以上时，HABI才能表现出最优的溶解性和感光度。任一种连接位的单一物质的溶解性均远远小于上述混合光引发剂，而如果这四种连接位的总含量低于92％，则感光度有明显变低的趋势。
代表性地，现有技术中，CN1292892A提到了一种用于光刻胶光聚合体系中的HABI类光引发剂，即2,2’,5-三(邻-氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,2-二咪唑，通常被称为“TCDM-HABI”，该文献中提到，使用至少含有一个亲水取代基(如甲氧基)的HABI能够大大减少循环使用的显影液中的淤渣量。然而申请人研究发现，单一的2,-2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1,2’-二咪唑或2,-2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1’,2-二咪唑在丁酮或PGMEA中的溶解度很低，例如在PGMEA中2,-2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1,2’-二咪唑的溶解度不到3％；使用这两种单一HABI配制的感光性树脂组合物，显影时显影液中的淤渣量都远远达不到预期的效果。令人意外地，将2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1,2’-二咪唑、2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-2’,3-二咪唑、2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-2,3’-二咪唑、2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1’,2-二咪唑四者相混合时，该混合物在溶剂中的溶解度得到了极大提升。
作为本发明中使用的HABI类混合光引发剂，优选满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物在其中的总质量百分含量为95％以上，特别优选由满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物组成。
HABI类光引发剂是光刻胶领域公知的一类光引发剂，可通过三芳基咪唑类或取代三芳基咪唑类化合物的氧化偶合来制备，具体制备工艺可参照例如US3784557、US4622286和US4311783等现有技术中的记载(在此将其全文引入以作为参考)。在现有工艺的基础上，增加溶剂重结晶工艺，即 可方便地获得满足本发明上述组成要求的HABI类混合光引发剂。所述溶剂可以是甲苯、甲醇、乙酸乙酯、二氯甲烷、水中的一种或两种以上的组合物。非限制性地，HABI类混合光引发剂的制备同样可以借鉴申请人的在先申请(申请号为CN201811451262.4)中记载的内容，在此将其全文引入以一并作为参考。
申请人研究发现，HABI类化合物的光引发活性受其芳香环上取代基的电子效应和立体效应的影响。较为适宜地，用于合成本发明的HABI类混合光引发剂的三芳基咪唑类或取代三芳基咪唑类化合物中的2-位或2’-位芳基上至少有一个邻位取代基为吸电子取代基，4-位芳基或4’-位芳基或5-位芳基或5’-位芳基上至少有一个取代基有供电子取代基。通过控制这些取代基的摩尔比值，即其相对应的取代苯甲醛的摩尔比值(单一结构的双咪唑是由六个相同或不相同的取代苯甲醛反应合成的，通过控制这些取代苯甲醛的摩尔比值，即可得到特定摩尔消光系数的混合双咪唑)，能够得到特定摩尔消光系数的混合双咪唑。为确保在整个波长范围内具有良好的吸收，优选地，所述HABI类混合光引发剂在355-420nm处摩尔消光系数大于6000且小于13000。若引发剂的摩尔消光系数小于6000，引发剂的吸光度不足，组合物的固化速度变慢；若引发剂的摩尔消光系数大于13000，则会出现表层固化过快，深层固化不足导致图形缺陷。
容易理解的是，两个单咪唑偶合，其主要产物是其中一个咪唑上的含有氢的N与另一个咪唑上2位的C连接而成的混合物。当两个单咪唑相同时，若单咪唑为不对称结构，如下文的TCTM，由其自身偶合得到的产物结构中2’-1与2-1’结构相同，2’-3与2-3’的结构也相同，所以其主结构为2’-1和2-3’两种连接位的产物；当两个单咪唑不相同时，主产物结构为2-1’、2-3’、2’-1 和2’-3四种连接位的双咪唑化合物。
在上述特征限定范围内，示例性地，本发明的HABI类混合光引发剂可选自或包含下列组合中的至少一种：
Figure PCTCN2020081292-appb-000004
Figure PCTCN2020081292-appb-000005
Figure PCTCN2020081292-appb-000006
本发明中，含有上述HABI类混合光引发剂的感光性树脂组合物在355-420nm的波长范围内具有较高的的光敏性，从而可以适应现有的不同波长的LED光源，如365nm、385nm、395nm、405nm，使可光固化的组合物适用于多种类型的光成像设备。
在100重量份感光性树脂组合物中，HABI类混合光引发剂含量为0.1-20重量份，优选为1-15重量份，更优选2-10重量份。在此含量范围内，组合物能够表现出良好的体系相容性和优异的固化性能。
具有烯属不饱和双键的化合物
具有烯属不饱和双键的化合物可促使感光性树脂组合物成膜。
对具有烯属不饱和双键的化合物没有特别限定，只要在分子内具有至少一个乙烯性不饱和键的光聚合性化合物就可以使用。示例性地，可列举出：α,β-不饱和羧酸与多元醇反应而得的化合物、双酚A类(甲基)丙烯酸酯化合物、α,β-不饱和羧酸与含缩水甘油基的化合物反应而得的化合物、分子内具有氨酯键的(甲基)丙烯酸酯化合物等氨基甲酸酯单体、壬基苯氧基多乙烯氧基丙烯酸酯、γ-氯-β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基乙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、苯二甲酸类化合物、(甲基)丙烯酸烷基酯等。这些化合物可以单独使用，也可两种以上组合使用。
作为上述α,β-不饱和羧酸与多元醇反应而得的化合物，可例举出：亚乙基数为2-14的聚乙二醇二(甲基)丙烯酸酯、亚丙基数为2-14的聚丙二醇二(甲基)丙烯酸酯、亚乙基数为2-14且亚丙基数为2-14的聚亚乙基·聚亚丙基二醇二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、EO改性三羟甲基丙烷三(甲基)丙烯酸酯、PO改性三羟 甲基丙烷三(甲基)丙烯酸酯、EO,PO改性三羟甲基丙烷三(甲基)丙烯酸酯、四羟甲基甲烷三(甲基)丙烯酸酯、四羟甲基甲烷四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、聚丙二醇单(甲基)丙烯酸酯、聚乙二醇单(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。在这里，“EO”表示环氧乙烷，经EO改性的化合物是指具有氧化乙烯基的嵌段结构的化合物。“PO”表示环氧丙烷，经PO改性的化合物是指具有氧化丙烯基的嵌段结构的化合物。
作为上述双酚A类(甲基)丙烯酸酯化合物，可例举出：2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基多丙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基多丁氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基多乙氧基多丙氧基]苯基}丙烷等。作为上述2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷，可例举出：2,2-双{4-[(甲基)丙烯酰氧基二乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基三乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基四乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基五乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基六乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基七乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基八乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基九乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十一乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十二乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十三乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十四乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十五乙氧基]苯基}丙烷、2,2-双{4-[(甲基)丙烯酰氧基十六乙氧基]苯基} 丙烷等。上述2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷的1分子内的氧化乙烯基数优选为4-20，更优选为8-15。这些化合物可以单独使用，也可两种以上组合使用。
作为上述分子内具有氨酯键的(甲基)丙烯酸酯化合物，可例举出：在β位具有OH基的(甲基)丙烯酸类单体和二异氰酸酯化合物(异佛尔酮二异氰酸酯、2,6-甲苯二异氰酸酯、2,4-甲苯二异氰酸酯、1,6-六亚甲基二异氰酸酯等)的加成反应产物、三[(甲基)丙烯酰氧基四亚乙基二醇异氰酸酯]六亚甲基异氰脲酸酯、EO改性氨酯二(甲基)丙烯酸酯、PO改性氨酯二(甲基)丙烯酸酯、EO,PO改性氨酯二(甲基)丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。
作为上述壬基苯氧基多乙烯氧基丙烯酸酯，可例举出：壬基苯氧基四乙烯氧基丙烯酸酯、壬基苯氧基五乙烯氧基丙烯酸酯、壬基苯氧基六乙烯氧基丙烯酸酯、壬基苯氧基七乙烯氧基丙烯酸酯、壬基苯氧基八乙烯氧基丙烯酸酯、壬基苯氧基九乙烯氧基丙烯酸酯、壬基苯氧基十乙烯氧基丙烯酸酯、壬基苯氧基十一乙烯氧基丙烯酸酯等。这些化合物可以单独使用，也可两种以上组合使用。
作为上述苯二甲酸类化合物，可例举出：γ-氯-β-羟基丙基-β’-(甲基)丙烯酰氧基乙基邻苯二甲酸酯、β-羟基烷基-β’-(甲基)丙烯酰氧基烷基邻苯二甲酸酯等。这些化合物可以单独使用，也可两种以上组合使用。
作为上述(甲基)丙烯酸烷基酯，可例举出：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸羟甲酯、(甲 基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸苄基酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸异辛酯、乙氧基化壬基酚(甲基)丙烯酸酯、丙二醇聚丙烯醚二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二(甲基)丙烯酸酯、乙氧基化聚四氢呋喃二醇二(甲基)丙烯酸酯、乙氧基化聚丙二醇二(甲基)丙烯酸酯等。其中，优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、三羟甲基丙烷三(甲基)丙烯酸酯、乙氧基化三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧化季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六丙烯酸酯。这些化合物可以单独使用，也可两种以上组合使用。
从提高密合性的角度来看，所述具有烯属不饱和双键的化合物优选双酚A类(甲基)丙烯酸酯化合物和分子内具有氨酯键的(甲基)丙烯酸酯化合物。从可以提高灵敏度和解析度的角度来看，优选双酚A类(甲基)丙烯酸酯化合物。作为双酚A类(甲基)丙烯酸酯化合物的市售品，示例性地，有2,2-双{4-[(甲基)丙烯酰氧基多乙氧基]苯基}丙烷(新中村化学工业株式会社制，BPE-200)、2,2-双{4-[(甲基)丙烯酰氧基多丙氧基]苯基)丙烷(新中村化学工业株式会社制，BPE-5000；日立化成株式会社制，FA-321M)、2,2-双{4-[(甲基)丙烯酰氧基多丁氧基]苯基}丙烷(新中村化学工业株式会社，BPE-1300)等。
在100重量份感光性树脂组合物中，具有烯属不饱和双键的化合物的含量为25-99重量份，优选为55-90重量份。
供氢体
本发明的感光性树脂组合物还包括供氢体。双咪唑类化合物经光照后 裂解，产生的单咪唑自由基体积较大，位阻效应使得活性较小，很难单独引发单体聚合，而如果和供氢体配合使用，则单咪唑自由基容易夺取供氢体上的活泼氢，产生新的活性自由基，进而引发单体聚合。
只要是具有上述特性的供氢体，在具体种类方面就没有特别限制。非限制性地，适用的供氢体可以是胺或胺改性化合物、硫醇类化合物，它们具有与杂原子相邻的碳连接的有效氢。这些化合物可单独使用，或以其中的两种以上组合使用。
示例性地，所述胺化合物可以是脂族胺、环脂族胺、芳族胺、芳族-脂族胺、杂环胺、低聚胺或者聚合胺。它们可以是伯胺、仲胺或者叔胺，例如丁基胺、二丁基胺、三丁基胺、环己胺、苄基二甲基胺、二环己胺、N-苯基甘氨酸、三乙胺、苯基-二乙醇胺、三乙醇胺、哌啶、哌嗪、吗啉、吡啶、喹啉、二甲氨基苯甲酸酯、米蚩酮(Michler’sketone)(4,4'-二-二甲基氨基二苯甲酮)、及相应衍生物。
胺改性化合物如胺-改性的丙烯酸酯化合物可用作供氢体。这种胺-改性的丙烯酸酯化合物的实例包括通过与伯胺或仲胺反应改性的丙烯酸酯，例如可以是US3,844,916、EP280222、US5,482,649或US5,734,002中公开的那些，在此将其全文引入以作为参考。
非限制性地，优选的胺或胺改性化合物有：EsacureA198(双-N,N-[4-二甲基氨基苯甲酰基)氧代乙烯-1-基]-甲基胺)和EsacureEDB(乙基-4-二甲基氨基苯甲酸酯)(两者都由意大利蓝宝迪有限公司(LambertiS.p.A.)出售)，2-乙基己基-4-二甲基氨基苯甲酸酯和N-苯基甘氨酸。
硫醇类化合物可以是一级硫醇、二级硫醇和多官能硫醇，优选二级硫醇和多官能硫醇。示例性地，硫醇类化合物可以是：2-巯基苯并噻唑(MBO)、 2-巯基苯并咪唑(MBI)、十二烷基硫醇、乙二醇双(3-巯基丁酸酯)、1,2-丙二醇双(3-巯基丁酸酯)、二乙二醇双(3-巯基丁酸酯)、丁二醇双(3-巯基丁酸酯)、辛二醇双(3-巯基丁酸酯)、三羟甲基丙烷三(3-巯基丁酸酯)、季戊四醇四(3-巯基丁酸酯)、二季戊四醇六(3-巯基丁酸酯)、乙二醇双(2-巯基丙酸酯)、丙二醇双(2-巯基丙酸酯)、二乙二醇双(2-巯基丙酸酯)、丁二醇双(2-巯基丙酸酯)、辛二醇双(2-巯基丙酸酯)、三羟甲基丙烷三(2-巯基丙酸酯)、季戊四醇四(3-巯基丙酸酯)、二季戊四醇六(2-巯基丙酸酯)、乙二醇双(3-巯基异丁酸酯)、1,2-丙二醇双(3-巯基异丁酸酯)、二乙二醇双(3-巯基异丁酸酯)、丁二醇双(3-巯基异丁酸酯)、辛二醇双(3-巯基异丁酸酯)、三羟甲基丙烷三(3-巯基异丁酸酯)、季戊四醇四(3-巯基异丁酸酯)、二季戊四醇六(3-巯基异丁酸酯)、乙二醇双(2-巯基异丁酸酯)、1,2-丙二醇双(2-巯基异丁酸酯)、二乙二醇双(2-巯基异丁酸酯)、丁二醇双(2-巯基异丁酸酯)、辛二醇双(2-巯基异丁酸酯)、三羟甲基丙烷三(2-巯基异丁酸酯)、季戊四醇四(2-巯基异丁酸酯)、二季戊四醇六(2-巯基异丁酸酯)、乙二醇双(4-巯基戊酸酯)、1,2-丙二醇双(4-巯基异戊酸酯)、二乙二醇双(4-巯基戊酸酯)、丁二醇双(4-巯基戊酸酯)、辛二醇双(4-巯基戊酸酯)、三羟甲基丙烷三(4-巯基戊酸酯)、季戊四醇四(4-巯基戊酸酯)、二季戊四醇六(4-巯基戊酸酯)、乙二醇双(3-巯基戊酸酯)、1,2-丙二醇双(3-巯基戊酸酯)、二乙二醇双(3-巯基戊酸酯)、丁二醇双(3-巯基戊酸酯)、辛二醇双(3-巯基戊酸酯)、三羟甲基丙烷三(3-巯基戊酸酯)、季戊四醇四(3-巯基戊酸酯)、二季戊四醇六(3-巯基戊酸酯)等脂肪族二级/多官能硫醇化合物；芳香族二级/多官能硫醇化合物的例子可列举：邻苯二甲酸二(1-巯基乙酯)、邻苯二甲酸二(2-巯基丙酯)、邻苯二甲酸二(3-巯基丁酯)、邻苯二甲酸二(3-巯基异丁酯)等。其中特别适宜的是乙二醇双(3-巯基丁酸酯)、 1,2-丙二醇双(3-巯基丁酸酯)、乙二醇双(2-巯基异丁酸酯)、1,2-丙二醇双(2-巯基异丁酸酯)、季戊四醇四(3-巯基丙酸酯)。
在100重量份感光性树脂组合物中，供氢体的含量为0.01-15重量份，优选为0.1-15重量份，更优选为0.1-10重量份，所述供氢体与通式(I)所示的HABI类混合光引发剂的重量份比值优选为1:20-1:3。
其它任选的光引发剂和/或增感剂
任选地，本发明的感光性树脂组合物中还可含有其它光引发剂和/或增感剂，以通过共同/协同效应来更加灵活地调整感光性树脂组合物的感光度。
所述其它光引发剂和/或增感剂可包括(但不限于)：双咪唑类、吡唑啉类、芳香族酮类、蒽醌类、苯偶姻和苯偶姻烷基醚类、肟酯类、三嗪类、三苯胺类、香豆素类、噻吨酮类、吖啶类及其它本领域技术人员已知的光引发剂。这些化合物可以单独使用，也可以两种以上组合使用。
示例性地，双咪唑类化合物包括：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’,5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,1’-二咪唑、2,2’,5-三(2-氟苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-二咪唑、2,2'-二(2,4-二氯苯基)-4,4',5,5'-四苯基-二咪唑、2,2'-二(2-氟苯基)-4-(邻氯苯基)-5-(3,4-二甲氧基苯基)-4’,5'-二苯基-二咪唑、2,2’-二(2-氟苯基)-4,4’,5,5’-四苯基-二咪唑、2,2’-二(2-甲氧基苯基)-4,4’,5,5’-四苯基-二咪唑、2,2'-二(2-氯-5-硝基苯基)-4,4'-二(3,4-二甲氧基苯基)-5,5'-二(邻氯苯基)-二咪唑、2,2'-二(2-氯-5-硝基苯基)-4-(3,4-二甲氧基苯基)-5-(邻氯苯基)-4',5'-二苯基-二咪唑、2,2'-二(2,4-二氯苯基)-4,4’-二(3，4-二甲氧基苯基)-5,5’-二(邻氯苯基)-二咪唑、2-(2,4-二氯苯基)-4-(3,4-二甲氧基苯基)-2',5-二(邻氯苯基)-4’,5’-二苯基-二咪唑、2-(2,4-二氯苯基)-2’-(邻氯苯基)-4,4’，5,5’- 四苯基-二咪唑、2,2'-二(2,4-二氯苯基)-4,4’,5,5’-四苯基-二咪唑及其相似物。这些双咪唑类化合物可以单独使用，也可以两种以上组合使用。
示例性地，吡唑啉类化合物包括：1-苯基-3-(4-叔丁基苯乙烯基)-5-(4-叔丁基苯基)吡唑啉、1-苯基-3-联苯基-5-(4-叔丁基苯基)吡唑啉、乙氧基化(9)三羟甲基吡唑啉酯、乙氧基化(10)双酚A吡唑啉酯及其相似物。这些吡唑啉类化合物可以单独使用，也可以两种以上组合使用。
示例性地，芳香族酮类化合物包括：苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、二苯甲酮、4-苯甲酰基二苯硫醚、4-苯甲酰基-4’-甲基二苯硫醚、4-苯甲酰基-4’-乙基二苯硫醚、4-苯甲酰基-4’-丙基二苯硫醚、4,4’-双(二乙基氨基)二苯甲酮、4-对甲苯巯基二苯甲酮、2,4,6-三甲基二苯甲酮、4-甲基二苯甲酮、4,4’-双(二甲氨基)二苯甲酮、4,4’-双(甲基、乙基氨基)二苯甲酮、苯乙酮二甲基缩酮、苯偶酰二甲基缩酮、α,α’-二甲基苯偶酰缩酮、α,α-二乙氧基苯乙酮、2-羟基-2-甲基-1-苯基丙酮、1-羟基环己基苯甲酮、2-羟基-2-甲基-1-对羟乙基醚基苯基丙酮、2-甲基1-(4-甲巯基苯基)-2-吗啉1-丙酮、2-苄基-2-二甲氨基-1-(4-吗啉苯基)1-丁酮、苯基双(2,4,6-三甲基苯甲酰基)氧膦、2,4,6(三甲基苯甲酰基)二苯基氧化膦、2-羟基-1-{3-[4-(2-羟基-2-甲基-丙酰基)-苯基]-1,1,3-三甲基-茚-5-基}-2-甲基丙酮；和2-羟基-1-{1-[4-(2-羟基-2-甲基-丙酰基)-苯基]-1,3,3-三甲基-茚-5-基}-2-甲基丙酮、1-(4-异丙基苯基)-2-羟基-2-甲基丙-1-酮、4-(2-羟基乙氧基)-苯基-(2-羟基-2-丙基)酮及其相似物。这些芳香族酮类化合物可以单独使用，也可以两种以上组合使用。
示例性地，蒽醌类化合物包括：2-苯基蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、2,3-二甲基蒽醌、2-乙基蒽-9,10-二乙酯、1,2,3-三甲基蒽 -9,10-二辛脂、2-乙基蒽-9,10-二(4-氯丁酸甲酯)、2-(3-((3-乙基氧杂环丁烷-3-基)甲氧基)-3-氧代丙基)蒽-9,10-二乙酯、9,10-二丁氧基蒽、9,10-二乙氧基-2-乙基蒽、9,10-二(3-氯丙氧基)蒽、9,10-二(2-羟基乙巯基)蒽、9,10-二(3-羟基-1-丙巯基)蒽及其相似物。这些蒽醌类化合物可以单独使用，也可以两种以上组合使用。
示例性地，苯偶姻和苯偶姻烷基醚类化合物包括：苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻苯基醚及其相似物。这些苯偶姻和苯偶姻烷基醚类化合物可以单独使用，也可以两种以上组合使用。
示例性地，肟酯类化合物包括：1-(4-苯硫基苯基)-正辛烷-1,2-二酮-2-苯甲酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-乙烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-丁烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-丙烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-1-环己基-甲烷-1-酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-3-环戊基-丙烷-1-酮-乙酸肟酯、1-(4-苯硫基苯基)-(3-环戊基)-丙烷-1，2-二酮-2-苯甲酸肟酯、1-(4-苯硫基苯基)-(3-环己基)-丙烷-1，2-二酮-2-环己基甲酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-苯甲酸肟酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基丙酮)-1-肟乙酸酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基丙酮)-1-肟环己基甲酸酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基丙酮)-1-肟环己基甲酸酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-(3-环戊基)-丙烷-1,2-二酮-2-邻甲基苯甲酸肟酯、1-(4-苯硫基苯基)-(3-环戊基)-丙烷-1,2-二酮-2-环 己基甲酸肟酯、1-(4-噻吩甲酰基-二苯硫醚-4’-基)-3-环戊基-丙烷-1-酮-乙酸肟酯、1-(4-苯甲酰基二苯硫醚)-(3-环戊基)-丙烷-1,2-二酮-2-肟乙酸酯、1-(6-硝基-9-乙基咔唑-3-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(6-邻甲基苯甲酰基-9-乙基咔唑-3-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(6-噻吩甲酰基-9-乙基咔唑-3-基)-(3-环己基丙酮)-1-肟乙酸酯、1-(6-呋喃糠甲酰基-9-乙基咔唑-3-基)-(3-环戊基丙酮)-1-肟乙酸酯、1,4-二苯基丙烷-1,3-二酮-2-乙酸肟酯、1-(6-糠酰基-9-乙基咔唑-3-基)-(3-环己基)-丙烷-1,2-二酮-2-乙酸肟酯、1-(4-苯硫基苯基)-(3-环已基)-丙烷-1，2-二酮-2-乙酸肟酯、1-(6-呋喃糠甲酰基-9-乙基咔唑-3-基)-(3-环己基丙酮)-1-肟乙酸酯、1-(4-苯硫基苯基)-(3-环已基)-丙烷-1，2-二酮-3-苯甲酸肟酯、1-(6-噻吩甲酰基-9-乙基咔唑-3-基)-(3-环己基)-丙烷-1，2-二酮-2-乙酸肟酯、2-((苯甲酰氧基)亚氨基)-1-苯基丙烷-1-酮、1-苯基-1,2-丙二酮-2-(氧代乙酰基)肟、1-(4-苯硫基苯基)-2-(2-甲基苯基)-乙烷-1,2-二酮-2-乙酸肟酯、1-(9,9-二丁基-7-硝基芴-2-基)-3-环己基-丙烷-1-酮-乙酸肟酯、1-(4-(4-(噻吩-2-甲酰基)苯硫基)苯基)-3-环戊基丙烷-1,2-二酮-2-乙酸肟酯、1-(9,9-二丁基-2-基)-3-环己基丙基丙烷-1,2-二酮-2-乙酸肟酯、1-(6-(2-(苯甲酰氧基亚氨基)-3-环己基丙基-9-乙基咔唑-3-基)辛烷-1,2-二酮-2-苯甲酸肟酯、1-(7-硝基-9,9-二烯丙基芴-2-基)-1-(2-甲基苯基)甲酮-乙酸肟酯、1-(6-(2-甲基苯甲酰基)-9-乙基咔唑-3-基)-3-环戊基-丙烷-1-酮-苯甲酸肟酯、1-(7-(2-甲基苯甲酰基)-9,9-二丁基芴-2-基)-3-环己基丙烷-1,2-二酮-2-乙酸肟酯、1-(6-(呋喃-2-甲酰基)-9-乙基咔唑-3-基)-3-环己基丙烷-1,2-二酮-2-乙氧甲酰肟酯及其相似物。这些肟酯类化合物可以单独使用，也可以两种以上组合使用。
示例性地，三嗪类化合物包括：2-(4-乙基联苯)-4,6-双(三氯甲基)-1,3,5-三嗪、2-(3,4-亚甲氧基苯基)-4,6-双(三氯甲基)-1,3,5-三嗪、3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、1,1,1,3,3,3-六氟异丙基-3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸酯、乙基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、2-乙氧基乙基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、环己基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、芐基-2-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}乙酸酯、3-{氯-4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙酸、3-{4-[2,4-双(三氯甲基)-s-三嗪-6-基]苯硫基}丙醯胺、2,4-双(三氯甲基)-6-p-甲氧基苯乙烯基-s-三嗪、2,4-双(三氯甲基)-6-(1-p-二甲基胺基苯基)-1,3,-丁二烯基-s-三嗪、2-三氯甲基-4-胺基-6-p-甲氧基苯乙烯基-s-三嗪及其相似物。这些三嗪类化合物可以单独使用，也可以两种以上组合使用。
示例性地，三苯胺类化合物包括：N,N-双-[4-(2-苯乙烯基-1-基)-苯基]-N,N-双(2-乙基-6甲基苯基)-1,1-双苯基-4,4-二胺、N,N-双-[4-(2-苯乙烯基-1-基)-4′-甲基苯基]-N,N-双(2-乙基-6甲基苯基)-1,1-双苯基-4,4-二胺及其相似物。这些三苯胺类化合物可以单独使用，也可以两种以上组合使用。
示例性地，香豆素类化合物包括：3,3’-羰基双(7-二乙胺香豆素)、3-苯甲酰基-7-二乙胺香豆素、3,3’-羰基双(7-甲氧基香豆素)、7-(二乙氨基)-4-甲基香豆素、3-(2-苯并噻唑)-7-(二乙基胺基)香豆素、7-(二乙氨基)-4-甲基-2H-1-苯并吡喃-2-酮(7-(二乙氨基)-4-甲基香豆素)、3-苯甲酰基-7-甲氧基香豆素及其相似物。这些香豆素类化合物可以单独使用，也可以两种以上组合使用。
示例性地，噻吨酮类化合物包括：噻吨酮、2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2,4-二异丙基噻吨酮、2-氯噻吨酮、1-氯-4-丙氧基噻吨酮、异丙基噻吨酮、二异丙基噻吨酮及相似物。这些噻吨酮类化合物可以单独使用，也可以两种以上组合使用。
示例性地，吖啶类化合物包括：9-苯基吖啶、9-对甲基苯基吖啶、9-间甲基苯基吖啶、9-邻氯苯基吖啶、9-邻氟苯基吖啶、2-乙基-2-(羟甲基)-1,3-丙二醇醚环乙烷醚的[4-(9-吖啶基)苯氧基]乙酸酯(即PAD107，产自常州强力电子新材料股份有限公司)、1,7-二(9-吖啶基)庚烷、9-乙基吖啶、9-(4-溴苯基)吖啶、9-(3-氯苯基)吖啶、1,7-双(9-吖啶)庚烷、1,5-双(9-吖啶戊烷)、1,3-双(9-吖啶)丙烷及其相似物。这些吖啶类化合物可以单独使用，也可以两种以上组合使用。
优选地，在100重量份感光性树脂组合物中，所述其它光引发剂和/或增感剂的含量为不超过8重量份。
其它任选的助剂
除了上述各组分，任选的，本发明的感光性树脂组合物中还可以根据需要包含适量的其它助剂。示例性地，助剂可以包括有机溶剂、染料、颜料、光显色剂、填充剂、增塑剂、稳定剂、涂布助剂、剥离促进剂等中的至少一种。
作为有机溶剂，只要能够溶解前述组分即可，示例性地，可以是二醇醚系溶剂、醇系溶剂、酯系溶剂、酮系溶剂、酰胺系溶剂、含氯溶剂等，优选特别考虑着色剂、碱可溶性聚合物的溶解性、涂布性、安全性等因素来进行选择。优选地，有机溶剂可以是乙基溶纤剂(乙二醇单乙基醚)、甲基溶纤剂(乙二醇单甲基醚)、丁基溶纤剂(乙二醇单丁基醚)、甲基甲氧基丁醇 (3-甲基-3-甲氧基丁醇)、丁基卡必醇(二甘醇单丁基醚)、乙二醇单乙基醚乙酸酯、乙二醇单叔丁基醚、丙二醇单甲基醚乙酸酯、丙二醇单甲基醚(1-甲氧基-2-丙醇)、丙二醇单乙基醚(1-乙氧基-2-丙醇)、丙二醇单乙基醚乙酸酯、乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸溶纤剂(乙二醇单甲基醚乙酸酯)、乙酸甲氧基丁酯(乙酸3-甲氧基丁酯)、乙酸3-甲基-3-甲氧基丁酯、3-乙氧基丙酸乙酯(EEP)、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、2-丁酮(MEK)、甲基异丁基酮(MIBK)、环己酮、环戊酮、二丙酮醇(4-羟基-4-甲基-2-戊酮)、异佛尔酮(3,5,5-三甲基-2-环己烯-1-酮)、二异丁基酮(2,6-二甲基-4-庚酮)、N-甲基吡咯烷酮(4-甲基氨基内酰胺或NMP)、甲醇、乙醇、异丙醇、正丙醇、异丁醇、正丁醇等。这些溶剂可单独使用，或以其中两种以上组合使用。
作为染料、颜料及光显色剂，示例性地，可以是：三(4-二甲基氨基苯基)甲烷、三(4-二甲基氨基-2甲基苯基)甲烷、荧烷染料、甲苯磺酸一水合物、碱性品红、酞菁绿及酞菁蓝等酞菁系、金胺碱、副品红、结晶紫、甲基橙、尼罗蓝2B、维多利亚蓝、孔雀绿、金刚绿、碱性蓝20、艳绿、伊红、乙基紫、赤藓红钠盐B、甲基绿、苯酚酞、茜素红S、百里香酚酞、甲基紫2B、喹那定红、玫瑰红钠琼脂、米塔尼尔黄、百里香酚磺酞、二甲苯酚蓝、甲基橘、橘IV、二苯基流卡巴腙、2,7-二氯荧光素、泛甲基红、刚果红、本佐红紫4B、α-萘基红、非那西汀、甲基紫、维多利亚纯蓝BOH、罗丹明6G、二苯基胺、二苄基苯胺、三苯基胺、二乙基苯胺、二-对伸二胺、对甲苯胺、苯并三氮唑、甲基苯丙三唑、4,4’-联二胺、邻氯苯胺、白色结晶紫、白色孔雀绿、白色苯胺、白色甲基紫、偶氮系等有机颜料，二氧化钛等无机颜料。在具有良好对比度的考量下，优选使用三(4-二甲基氨基苯基)甲烷 (即隐色结晶紫，LCV)。这些染料、颜料及光显色剂可以单独一种使用，也可两种以上混合使用。
作为填充剂，示例性地，可以是：二氧化硅、氧化铝、滑石、碳酸钙、硫酸钡等填充剂(不包含上述无机颜料)。填充剂可以单独一种使用，也可两种以上混合使用。
作为增塑剂，示例性地，可以是：邻苯二甲酸二丁酯、邻苯二甲酸二庚酯、邻苯二甲酸二辛酯、邻苯二甲酸二烯丙酯等邻苯二甲酸酯，三甘醇二乙酸酯、四乙二醇二乙酸酯等乙二醇酯，对甲苯磺酰胺、苯磺酰胺、正丁基苯磺酰胺等磺酰胺类，磷酸三苯酯、三甲基磷酸酯、三乙基磷酸酯、三苯基磷酸酯、三甲苯基磷酸酯、三二甲苯基磷酸酯、甲苯基二苯基磷酸酯、三二甲苯基磷酸酯、2-萘基二苯基磷酸酯、甲苯基二2,6-二甲苯基磷酸酯、芳香族缩合磷酸酯、三(氯丙基)磷酸酯、三(三溴新戊基)磷酸酯、含卤缩合磷酸酯，二辛酸三甘醇酯，二(2-乙基己酸)三甘醇酯、二庚酸四甘醇酯、癸二酸二乙酯、辛二酸二丁酯、磷酸三(2-乙基乙酯)、Brij30[C 12H 25(OCH 2CH 2) 4OH]、和Brij35[C 12H 25(OCH 2CH 2) 20OH]等。增塑剂可以单独一种使用，也可两种以上混合使用。
作为稳定剂，示例性地，可以是：氢醌、1,4,4-三甲基-重氮二环(3.2.2)-壬-2-烯-2,3-二氧化物、1-苯基-3-吡唑烷酮、对甲氧基苯酚、烷基和芳基取代的氢醌和醌、叔丁基邻苯二酚、1,2,3-苯三酚、树脂酸铜、萘胺、β-萘酚、氯化亚铜、2,6-二叔丁基对甲酚、吩噻嗪、吡啶、硝基苯、二硝基苯、对甲苯醌和氯醌等。稳定剂可以单独一种使用，也可两种以上混合使用。
作为涂布助剂，从安全性、通用性方面考虑，可以是：丙酮、甲醇、甲基醇、乙基醇、异丙基醇、甲基乙基酮、丙二醇单甲基醚乙酸酯、乳酸 乙酯、环己酮、γ-丁内酯、二氯甲烷等。涂布助剂可以单独一种使用，也可两种以上混合使用。
作为剥离促进剂，示例性地，可例举出：苯磺酸、甲苯磺酸、二甲苯磺酸、苯酚磺酸，甲基、丙基、庚基、辛基、癸基、十二烷基等烷基苯磺酸等。剥离促进剂可以单独一种使用，也可两种以上混合使用。
优选地，在100重量份感光性树脂组合物中，助剂的总含量不超过10重量份。
<UVLED光固化应用>
本发明所述的应用中，LED光源的波长在355-420nm范围内，可以是365nm、385nm、395nm、405nm等。
本发明的上述感光性树脂组合物可作为油墨和涂料组合物，用于涂覆金属表面、木材表面、纸表面和塑料表面等。具体应用时，可使用柔版印刷、胶版印刷、凹版印刷或喷墨印刷方法涂布油墨或涂料组合物，然后经辐射固化。本发明的上述感光性树脂组合物可以在氧的存在下固化，从而排除了在固化期间对提供惰性无氧环境以防止氧抑制的需要。
附图说明
图1是产物A1的高效液相色谱图。
图2是BCIM经单晶衍射得到的结构谱图。
具体实施方式
以下结合具体实施例对本发明作进一步详细说明，但不应将其理解为对本发明保护范围的限制。
1.HABI类混合光引发剂的制备
1.1 HABI类混合光引发剂A1的制备
氮气保护下，向1L的四口烧瓶中投入31.8g 2-(邻氯苯基)-4,5-二苯基-咪唑(INC)、51.3g 2,5-二(邻氯苯基)-4-(4,5-二甲氧基苯基)-咪唑(TAI)、106g 30％液碱、4.0g四丁基溴化铵和300g甲苯，加热搅拌，并在60-65℃时滴加130g次氯酸钠(11％浓度)，滴加结束后保温反应，取样通过HPLC进行中控，至INC和TAI均小于1％，反应完全，结束保温。
保温反应结束后，用100g纯水洗涤四次，然后用20g甲苯萃取一次水层，将有机层进行减压蒸馏。向蒸馏得到的物料中加入70g甲醇，加热搅拌至溶清，再将溶清液滴加至由30g甲醇和50g纯水配置而成的重结晶溶液中，滴加结束后进行淋洗、抽干、烘料，得到79.1g产物A1。
图1是产物A1的高效液相色谱图。分析结果显示，2-1’、2-3’、2’-1和2’-3四种连接位的产品峰总含量为92.5％。
产物A1是由两个不同的单咪唑(即INC、TAI)经两两自身偶合和相互偶合得到的混合物，包括BCIM、TCTM和TCDM。为精确验证产物的结构组成，分别对成分BCIM、TCTM和TCDM进行验证分析。
通过单咪唑自身偶合、柱层析、色谱分离等手段，分别得到纯的BCIM、TCTM和TCDM，分别进行结构确认。
BCIM在液相中只有一个峰，但通过单晶衍射得到两个峰形，见附图2。结合结构特征可以确定，两个单咪唑偶合其主要产物是其中一个咪唑上的含有氢的N与另一个咪唑上2位的C连接而成的混合物，由此表明BCIM的结构为本发明中所述的2’-1和2’-3两种连接位。
合成BCIM的咪唑是INC，属于对称型咪唑，所以偶合得到的2’-1和2’-3极性相似，液相难以进行分离。并且由于INC的结构对称性，由其自身偶合得到的产物结构中2’-1与2-1’结构相同，2’-3与2-3’的结构也相同，所以BCIM主结构为2’-1和2’-3两种连接位的产物，结构式如下所示，分别为BCIM1：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-1,2’-二咪唑和BCIM2：2,2’-二(邻氯苯基)-4,4’,5,5’-四苯基-2’,3-二咪唑；
Figure PCTCN2020081292-appb-000007
同样，对分离得到的纯TCTM进行分析，主结构为四个连接位产品，进行LCMS确认结构。质谱分析借助仪器附带软件得到849与850分子碎片峰，产品的分子量为848，与T+1和T+2吻合，证明这四个产物结构相仿，分子量相同。合成TCTM的单咪唑TAI属于不对称的单咪唑，所以TAI存在两种构型，TAI1和TAI2，如下所示：
Figure PCTCN2020081292-appb-000008
TCTM由不对称的单咪唑偶合合成，理论存在八种1-2和2-3连接位连接的主结构，但对于自身偶合的单咪唑，结构中的2’-1与2-1’结构相同，2’-3与2-3’的结构也相同，所以对于TCTM来说，其实际存在四种1-2和2-3连接位连接的主结构，其组成分别为：
TCTM1：2,2’,5,5'-四(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-2’,3-二咪唑，TCTM2：2,2’,4,5'-四(邻氯苯基)-4’,5-双(3,4-二甲氧基苯基)-1,2’-二咪唑，TCTM3：2,2’,5,5'-四(邻氯苯基)-4,4’-双(3,4-二甲氧基苯基)-1,2’-二咪唑，TCTM4：2,2’,4,5'-四(邻氯苯基)-4’,5-双(3,4-二甲氧基苯基)-2’,3-二咪唑，结构如下所示：
Figure PCTCN2020081292-appb-000009
Figure PCTCN2020081292-appb-000010
TCDM是由INC与TAI两两偶合而成，分离得到的纯TCDM在液相中主结构为四种连接位的产品，对四种连接位的产品进行LCMS确认结构。质谱分析借助仪器附带软件得到755与756分子碎片峰，产品的分子量为754，与T+1和T+2吻合，证明这四个产物结构相仿，分子量相同。TCDM由对称的咪唑INC与不对称的咪唑TAI两两连接而成，存在四种1-2和2-3连接位连接的主结构，其组成分别为：
TCDM1：2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1,2’-二咪唑，TCDM2：2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-2’,3-二咪唑，TCDM3：2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-2,3’-二咪唑，TCDM4：2,2',5-三(邻氯苯基)-4-(3,4-二甲氧基苯基)-4',5'-二苯基-1’,2-二咪唑，结构式如下：
Figure PCTCN2020081292-appb-000011
Figure PCTCN2020081292-appb-000012
综合上述实验分析确定，产物A1是由BCIM(BCIM1、BCIM2)、TCTM(TCTM1、TCTM2、TCTM3、TCTM4)和TCDM(TCDM1、TCDM2、TCDM3、TCDM4)组合而成，其中由2-1’、2-3’、2’-1和2’-3四种连接位构成的双咪唑化合物在A1中的含量为92.5％。
1.2 A2-A8的制备
参照A1的制备方法，分别制备得到A2-A8，各产品情况如下表1所示。
表1
Figure PCTCN2020081292-appb-000013
Figure PCTCN2020081292-appb-000014
摩尔消光系数测试方法为：
测试产品在0.01％乙腈下的吸光度，根据ε＝A/Cb计算，其中C为相对浓度(mol/L)，A为吸光度，ε为摩尔吸光系数(L/mol·cm)，b为样品池厚度(cm)。具体本发明的测试条件中，C为10 -4mol/L，b为1cm。
2.感光度测试
2.1待测样品的制备
按重量份99.5:0.5将Ebecryl605和Ebecryl350(赛特工业公司(CytecIndustriesInc.))混匀，再加入3重量份的光引发剂和1重量份的供氢体EsacureEDB(由蓝宝迪有限公司出售)，制备成待测组合物。
除了上述表1和2中的光引发剂之外，同时选用本领域中常用的两种光引发剂即异丙基噻吨酮(ITX)和三苯基氧化膦(TPO)作为对比。
2.2测试方法
将待测组合物样品置于FT-IR(FT-IR430-Jasco)的样品存放室中，并暴露于LED光源下(365、385、395或405nm)，LED光源距离样品65毫米并成30°的角度。
在光聚合时，通过傅里叶红外光谱仪采集IR光谱，并用IR软件测定分配给丙烯酸双键的1408cm -1和810cm -1处峰面积在光照前后的峰面积。计算峰面积的降低程度(％)，由此将聚合程度定量化，进而定量光引发剂的效率。峰面积的降低程度(％)越大，表示单位时间内的双键转化率越高，引发剂的感度越佳。
2.3测试结果
测试结果见下表，以3S内峰面积的降低程度(％)来表示。
表3
Figure PCTCN2020081292-appb-000015
Figure PCTCN2020081292-appb-000016
Figure PCTCN2020081292-appb-000017
从上表可以看出，本发明的上述HABI类混合光引发剂(A1、A2、A3、)具有与TPO、ITX类似的感光度，对比例(A4、A)由于溶解性偏低影响了在配方中的使用，对比例(A6、A7、A8)虽然溶解性与实施例相当，但相比实施例感光度偏低，达不到TPO、ITX的使用效果；对比例(A9、A10)由于取代位不符合本发明所述的取代规则，在UVLED下感度较低，难以应用。
结果表明，当以LED为光源，本发明的上述HABI类混合光引发剂在感光性树脂组合物中具有与现有技术相当的感光性能。
3.成膜性能测试
3.1待测样品的制备
以A1、A2、A3、A9为例，根据下面的配方配制样品，并对其成膜性能进行评价：
自由基聚合单体TMPTA         94重量份
光引发剂                    5重量份
N-PG(供氢体)                1重量份。
以商品化的TPO、ITX光引发剂作为对比。
3.2测试方法
将待测组合物样品避光搅拌均匀，取样于PET基板上，25#线棒涂布，形成厚度为25μm的涂膜，然后使用LED光源(辐射波长为385nm，曝光量240mj/cm 2)对涂膜进行辐射固化。
各配方的固化情况从表干和底干两方面来考察。参照漆膜干燥时间测试标准GB/T 1728-1979中指触法来评价表面固化情况，即用手指轻触涂层，以表面滑爽，不粘手表示表面固化完全；采用指抠法测量底部固化情况，即用指甲轻抠涂层，以无脱落，无露底现象表示底层固化完全。
通过肉眼观察固化膜的表面形貌，并通过扇闻法评价固化膜有无刺激性气味。表面越平整，说明与单体相容性越好；气味越低，说明挥发性越小。
黄变测试：用UVA(340)灯作为光源，将曝光后的固化膜试板置于温度为(120±5)℃、辐照度为0.68W/m2、干燥(无凝露)的荧光紫外老化机中，全过程保持连续光照168小时。光照结束后取出，与初始TPO曝光后 的试板做对照，用色差仪测量颜色变化，颜色变化值单位△E*。实测值越小，颜色越接近。
3.3测试结果
具体测试结果示于表4中。
表4
Figure PCTCN2020081292-appb-000018
从上述测试中可以看出，本发明的上述HABI类混合光引发剂无论与A9相比，还是与现有技术的TPO和ITX，其表干效果更优，且具有更低的气味和低黄变，使用更为安全。

Claims (15)

  1. HABI类混合光引发剂在UVLED光固化中的应用，其特征在于，使用的感光性树脂组合物包含下列组分：
    (a)0.1-20重量份的HABI类混合光引发剂，具有如通式(I)所示结构，其中含有2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物，且该四种连接位的双咪唑化合物在HABI类混合光引发剂中的总质量百分含量为92％以上，
    Figure PCTCN2020081292-appb-100001
    其中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6可以相同也可以不同，各自独立地表示取代或未取代的芳基；
    并且其中，2-位或2’-位芳基上至少有一个邻位取代基为吸电子取代基，4-位芳基或4’-位芳基或5-位芳基或5’-位芳基上至少有一个取代基有供电子取代基；
    所述HABI类混合光引发剂在355-420nm处摩尔消光系数大于6000且小于13000；
    (b)25-99重量份的至少一种具有烯属不饱和双键的化合物；
    (c)0.01-15重量份的供氢体，所述供氢体与通式(I)所示的HABI类混合光引发剂的重量比为1:20-1:1。
  2. 根据权利要求1所述的应用，其特征在于：通式(I)中，所述芳基是苯基。
  3. 根据权利要求1所述的应用，其特征在于：通式(I)中，芳基上的吸电子取代基选自卤素、硝基、氰基、胺基，芳基上的供电子取代基选自甲氧基、C 3-C 10的支链烷基或链烯基。
  4. 根据权利要求1或2所述的应用，其特征在于：通式(I)中，Ar 1、Ar 2、Ar 3、Ar 4、Ar 5、Ar 6中至少一个是含有卤素取代基的芳基；优选地，卤素取代基为氯。
  5. 根据权利要求1所述的应用，其特征在于：作为HABI类混合光引发剂，满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物在其中的总质量百分含量为95％以上。
  6. 根据权利要求1或5所述的应用，其特征在于：所述HABI类混合光引发剂由满足通式(I)所示结构的2-1’、2-3’、2’-1和2’-3四种连接位的双咪唑化合物组成。
  7. 根据权利要求1所述的应用，其特征在于：所述具有烯属不饱和双键的化合物选自α,β-不饱和羧酸与多元醇反应而得的化合物、双酚A类(甲基)丙烯酸酯化合物、α,β-不饱和羧酸与含缩水甘油基的化合物反应而得的化合物、分子内具有氨酯键的(甲基)丙烯酸酯化合物、壬基苯氧基多乙烯氧基丙烯酸酯、γ-氯-β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基乙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、β-羟基丙基-β’-(甲基)丙烯酰氧基乙基-邻苯二甲酸酯、苯二甲酸类化合物、(甲基)丙烯酸烷基酯。
  8. 根据权利要求1或7所述的应用，其特征在于：所述具有烯属不饱和双键的化合物选自双酚A类(甲基)丙烯酸酯化合物和分子内具有氨酯键的(甲基)丙烯酸酯化合物。
  9. 根据权利要求1所述的应用，其特征在于：所述供氢体是胺或胺改 性化合物、硫醇类化合物，它们具有与杂原子相邻的碳连接的有效氢。
  10. 根据权利要求9所述的应用，其特征在于：所述胺或胺改性化合物选自EsacureA198、EsacureEDB、2-乙基己基-4-二甲基氨基苯甲酸酯和N-苯基甘氨酸中的至少一种。
  11. 根据权利要求9所述的应用，其特征在于：所述硫醇类化合物选自乙二醇双(3-巯基丁酸酯)、1,2-丙二醇双(3-巯基丁酸酯)、乙二醇双(2-巯基异丁酸酯)、1,2-丙二醇双(2-巯基异丁酸酯)、季戊四醇四(3-巯基丙酸酯)中的至少一种。
  12. 根据权利要求1所述的应用，其特征在于：所述供氢体与通式(I)所示的HABI类混合光引发剂的重量份比值为1:20-1:3。
  13. 根据权利要求1所述的应用，其特征在于：所述感光性树脂组合物中还可含有其它光引发剂和/或增感剂。
  14. 根据权利要求1所述的应用，其特征在于：所述应用中，UVLED光源的波长在355-420nm范围内，包括365nm、385nm、395nm、405nm。
  15. 根据权利要求1所述的应用，其特征在于：所述感光性树脂组合物作为油墨和涂料组合物使用。
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