CN111752091A - Application of HABI mixed photoinitiator in UVLED photocuring - Google Patents

Application of HABI mixed photoinitiator in UVLED photocuring Download PDF

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CN111752091A
CN111752091A CN201910248385.6A CN201910248385A CN111752091A CN 111752091 A CN111752091 A CN 111752091A CN 201910248385 A CN201910248385 A CN 201910248385A CN 111752091 A CN111752091 A CN 111752091A
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habi
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CN111752091B (en
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钱晓春
杨金梁
严春霞
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Changzhou Zhengjie Intelligent Manufacturing Technology Co ltd
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Changzhou Green Photosensitive Materials Co ltd
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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

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Abstract

The invention discloses an application of a hexaarylbisimidazole mixed photoinitiator in UVLED photocuring. The photosensitive resin composition containing the specific HABI mixed photoinitiator has excellent comprehensive performance under an LED light source, good compatibility and high light sensitivity, can replace the traditional TPO and ITX initiators, solves the problem of surface dryness, and has the characteristics of no odor and low yellowing.

Description

Application of HABI mixed photoinitiator in UVLED photocuring
Technical Field
The invention belongs to the technical field of organic chemistry and photocuring, and particularly relates to an application of a HABI mixed photoinitiator in UVLED photocuring.
Background
With the development of photocuring technology, UVLED technology is gradually replacing the conventional high-pressure mercury lamp technology. UVLEDs have many advantages, such as long service life, low energy consumption, cold light sources, no mercury, stable light output, wide applicability, near zero maintenance cost, etc.
The most commonly used UVLED light sources have wavelengths between 355 and 420 nm. Absorption in this wavelength region is required as a photoinitiator for use in uv led technology, while good compatibility with other components of the photocurable system is required in view of the high concentrations of photoactive materials typically required for uv led applications. Currently, thioxanthones (such as isopropylthioxanthone ITX) and their derivatives, with acylphosphine oxides, are the most commonly used photoinitiators in this field. However, as a single-wavelength UVLED light source, a high-sensitivity photoinitiator, such as ITX, TPO, etc., is usually selected to match the wavelength of the UVLED light source, and the free radicals generated by the irradiation of light by these initiators have high activity and are easily quenched by oxygen in the air, so that it is a problem that needs to be solved urgently in this field to develop an initiator suitable for the UVLED light source and free from an exterior dry problem caused by oxygen inhibition. In addition, thioxanthones tend to yellow upon exposure, and it is difficult to control the color of the final image in image formation such as ink jet printing because of such unstable yellowing properties; acylphosphine oxide initiators, when used, produce moderately volatile aldehyde degradation products, produce undesirable odors, and can present health and safety concerns when used in large quantities. Therefore, in order to promote the development of the UVLED technology in the field of photocuring, it is urgently needed to develop a suitable photoinitiator with improved performance to meet the requirement of UVLED light source curing.
The bisimidazole photoinitiator is formed by coupling two single imidazoles, chemical bonds connecting the two imidazoles can be broken under the condition of illumination or heating to generate single imidazole free radicals, the free radicals serving as macromolecular free radicals can exist relatively stably and are not easily quenched by oxygen, and the bisimidazole photoinitiator is suitable for the fields of printing plate making, photosensitive imaging, printed circuit boards and the like. The bisimidazole photoinitiator can effectively solve the problems of surface dryness, smell, yellowing and the like generated in use, but due to the problems of poor solvent property and sensitivity or difficulty in simultaneous consideration, the application of the bisimidazole photoinitiator as a main initiator in the field of UVLED photocuring is not reported. How to apply the bisimidazole photoinitiator to a formula system taking an LED as a light source so as to solve the problems of surface dryness, odor and yellowing of the existing ITX and TPO becomes an important direction for the research in the field.
Disclosure of Invention
The invention aims to provide an application of a Hexaarylbisimidazole (HABI) mixed photoinitiator in UVLED photocuring. The photosensitive resin composition containing the specific HABI mixed photoinitiator has excellent comprehensive performance under an LED light source, good compatibility and high light sensitivity, can replace the traditional TPO and ITX initiators, solves the problem of surface dryness, and has the characteristics of no odor and low yellowing.
Specifically, the application of the HABI mixed photoinitiator in UVLED photocuring is characterized in that the used photosensitive resin composition comprises the following components:
(a)0.1 to 20 weight portions of HABI mixed photoinitiator which has the structure shown in the general formula (I) and contains 2 to 1 ', 2 to 3', 2 '-1 and 2' -3 double imidazole compounds of four connection sites, wherein the total mass percentage content of the four double imidazole compounds of the connection sites in the HABI mixed photoinitiator is more than 92 percent,
Figure RE-GDA0002084914610000031
wherein Ar is1、Ar2、Ar3、Ar4、Ar5、Ar6May be the same or different and each independently represents a substituted or unsubstituted aryl group;
wherein at least one ortho-position substituent on the 2-position or 2' -position aryl is an electron-withdrawing substituent, and at least one substituent on the 4-position aryl or 4' -position aryl or 5' -position aryl is provided with an electron-donating substituent;
the molar extinction coefficient of the HABI mixed photoinitiator at 355-420nm is more than 6000 and less than 13000;
(b)25 to 99 parts by weight of at least one compound having an ethylenically unsaturated double bond;
(c)0.01-15 parts by weight of hydrogen donor, wherein the weight ratio of the hydrogen donor to the HABI mixed photoinitiator shown in the general formula (I) is 1:20-1: 1.
In order to better explain the technical scheme of the present invention, each part (such as each component in the photosensitive resin composition) in the above application will be described separately.
< photosensitive resin composition >
In the UVLED photocuring application of the invention, the HABI type mixed photoinitiator and other components form a photosensitive resin composition and are used in the form of a composition.
HABI mixed photoinitiator
The HABI mixed photoinitiator has a structure shown as a general formula (I), wherein the HABI mixed photoinitiator contains 2-1 ', 2-3', 2 '-1 and 2' -3 double imidazole compounds at four connecting positions, the total mass percentage content of the four double imidazole compounds at the four connecting positions in the mixed photoinitiator is more than 92 percent,
Figure RE-GDA0002084914610000041
in the general formula (I), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Which may be the same or different, each independently represents a substituted or unsubstituted aryl group.
In the general formula (I), the electron-withdrawing substituent on the aryl is selected from halogen, nitro, cyano and amino, and the electron-donating substituent on the aryl is selected from methoxy and C3-C10A branched alkyl or alkenyl group of (a);
the bisimidazole compound satisfying four connection positions of 2-1 ', 2-3', 2 '-1 and 2' -3 of the structure shown in the general formula (I) is specifically the following structure:
Figure RE-GDA0002084914610000042
in the general formula (I), the aryl group is preferably a phenyl group.
The substituted aryl group may be mono-substituted or poly-substituted.
Preferably, the substituents on the aryl group may be halogen, nitro, cyano, amino, hydroxy, C1-C20Alkyl or alkenyl of, C1-C8Wherein the methylene group in each independent variable (i.e., each substituent) may be optionally substituted with oxygen, sulfur, an imine group.
More preferably, the substituents on the aryl group may be fluorine, chlorine, bromine, nitro, cyano, amino, hydroxy, C1-C10Alkyl of (2)Or alkenyl, C1-C5Wherein the methylene group in each independent variable may be optionally substituted with oxygen, sulfur, or an imine group.
Further preferably, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6At least one of which is an aryl group having a halogen substituent. Particularly preferably, the halogen substituent is chlorine.
The HABI type hybrid photoinitiator described herein is formed by coupling two triarylimidazoles (which may be the same or different depending on the substituents on the aryl groups). Due to the induction effect of the substituent on the benzene ring, the pi electron cloud density of the benzene ring is reduced, the benzene ring is twisted by the induction effect, the conjugated center on the imidazole ring is deviated, so that the substituted phenyl and the imidazole are not in the same plane (the triarylimidazole is in a curved surface state), and finally, when the two imidazoles are coupled, N, C connection presents different spatial configurations, thereby greatly influencing the performance of HABI.
In addition to the four linking sites 2-1 ', 2-3', 2 '-1, 2' -3 described above, the HABI compound represented by the general formula (I) may have 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 linking sites in structure. However, the applicant has found that HABI exhibits optimum solubility and sensitivity only when four kinds of linking sites 2-1 ', 2-3', 2 '-1, 2' -3 are present and the total content is more than 92% of the total amount of HABI. The solubility of the single substance of any of the linking sites is much smaller than that of the above-mentioned mixed photoinitiator, and if the total content of these four linking sites is less than 92%, the sensitivity tends to become significantly lower.
Typically, CN1292892A in the prior art mentions a HABI type photoinitiator for use in photo-polymerization systems for photoresists, i.e. 2,2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5' -diphenyl-1, 2-diimidazole, commonly known as "TCDM-HABI", which mentions that the use of HABI containing at least one hydrophilic substituent (e.g. methoxy) can greatly reduce the amount of sludge in the recycled developer. However, the applicant has found that the solubility of 2, -2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1, 2' -diimidazole alone or 2, -2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1', 2-diimidazole in butanone or PGMEA is low, for example the solubility of 2, -2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1, 2' -diimidazole in PGMEA is less than 3%; the amount of sludge in the developer during development was far from the expected effect using the photosensitive resin compositions formulated with these two single HABI. Surprisingly, 2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1, 2' -diimidazole, 2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-2', 3-diimidazole, 2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-2, 3' -diimidazole, 2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1', when the 2-diimidazole four phases are mixed, the solubility of the mixture in a solvent is greatly improved.
The HABI-based hybrid photoinitiator used in the present invention preferably contains 95% by mass or more of the bisimidazole compounds satisfying four types of 2-1 ', 2-3', 2 '-1 and 2' -3 of the linking sites represented by the general formula (I), and particularly preferably contains four types of the bisimidazole compounds satisfying four types of the linking sites represented by the general formula (I), 2-1 ', 2-3', 2 '-1 and 2' -3.
The HABI type photoinitiators are well known in the art of photoresists and may be prepared by oxidative coupling of triarylimidazoles or substituted triarylimidazoles, as described in the prior art, for example, in US3784557, US4622286 and US4311783 (the entire contents of which are incorporated herein by reference). On the basis of the prior art, a solvent recrystallization process is added, so that the HABI mixed photoinitiator meeting the composition requirements of the invention can be conveniently obtained. The solvent can be one or a combination of more than two of toluene, methanol, ethyl acetate, dichloromethane and water. The preparation of HABI-based hybrid photoinitiators is likewise described in the applicant's prior application (application No. CN201811451262.4), which is incorporated herein by reference in its entirety, without limitation.
The applicant researches and discovers that the photoinitiation activity of the HABI compound is influenced by the electronic effect and the steric effect of a substituent on an aromatic ring of the HABI compound. Preferably, at least one ortho-position substituent on 2-position or 2' -position aryl in the triarylimidazole or substituted triarylimidazole compound used for synthesizing the HABI mixed photoinitiator is an electron-withdrawing substituent, and at least one substituent on 4-position aryl or 4' -position aryl or 5' -position aryl has an electron-donating substituent. By controlling the molar ratio of the substituents, namely the molar ratio of the corresponding substituted benzaldehyde (the bisimidazole with a single structure is synthesized by reacting six same or different substituted benzaldehydes, and by controlling the molar ratio of the substituted benzaldehydes, the mixed bisimidazole with a specific molar extinction coefficient can be obtained), and the mixed bisimidazole with the specific molar extinction coefficient can be obtained. To ensure good absorption over the entire wavelength range, the molar extinction coefficient of the HABI-based hybrid photoinitiator at 355-420nm is preferably greater than 6000 and less than 13000. If 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 is slowed down; if the molar extinction coefficient of the initiator is greater than 13000, the surface layer may be cured too fast, and the deep layer may be cured insufficiently to cause pattern defects.
It is readily understood that the main product of the coupling of two mono-imidazoles is a mixture of the hydrogen-containing N on one of the imidazoles linked to the C at the 2-position on the other imidazole. When two single imidazoles are the same, if the single imidazole has an asymmetric structure, such as the following TCTM, the structures of 2 '-1 and 2-1' and 2 '-3 and 2-3' in the product structure obtained by coupling the single imidazole with itself are the same, so that the main structure thereof is a product of two connection sites of 2 '-1 and 2-3'; when the two monoimidazoles are different, the main product structure is a bisimidazole compound with four connection positions of 2-1 ', 2-3', 2 '-1 and 2' -3.
Within the above feature limitations, the HABI-based hybrid photoinitiators of the present invention may illustratively be selected from or comprise at least one of the following combinations:
TCTM：
Figure RE-GDA0002084914610000081
TCDM：
Figure RE-GDA0002084914610000091
HABI-B
Figure RE-GDA0002084914610000092
Figure RE-GDA0002084914610000101
HABI-C
Figure RE-GDA0002084914610000102
in the invention, the photosensitive resin composition containing the HABI mixed photoinitiator has higher photosensitivity in the wavelength range of 355-420nm, thereby being suitable for the existing LED light sources with different wavelengths, such as 365nm, 385nm, 395nm and 405nm, and the photocurable composition is suitable for various types of optical imaging equipment.
The content of the HABI type hybrid photoinitiator is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. Within this content range, the composition can exhibit good system compatibility and excellent curing properties.
Compounds having ethylenically unsaturated double bonds
The compound having an ethylenically unsaturated double bond can promote film formation of the photosensitive resin composition.
The compound having an ethylenically unsaturated double bond is not particularly limited, and a photopolymerizable compound having at least one ethylenically unsaturated bond in the molecule can be used. By way of example, mention may be made of: examples of the urethane monomer include a compound obtained by reacting an α, β -unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol a-based (meth) acrylate compound, a compound obtained by reacting an α, β -unsaturated carboxylic acid with a glycidyl group-containing compound, a urethane monomer such as a (meth) acrylate compound having a urethane bond in the molecule, nonylphenoxy polyethyleneoxy acrylate, γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, phthalic compounds, and alkyl (meth) acrylates. These compounds may be used alone or in combination of two or more.
Examples of the compound obtained by reacting the α, β -unsaturated carboxylic acid with a polyhydric alcohol include: polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, polyethylene-polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polypropylene glycol mono (meth) acrylate, polypropylene glycol di (meth) acrylate, polypropylene glycol, Polyethylene glycol mono (meth) acrylate, tripropylene glycol di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more. Here, "EO" represents ethylene oxide, and the EO-modified compound means a compound having a block structure of an oxyethylene group. "PO" represents propylene oxide, and a PO-modified compound means a compound having a block structure of an oxypropylene group.
Examples of the bisphenol a (meth) acrylate compound include: 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolypropoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolybutoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane and the like. Examples of the 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane include: 2, 2-bis {4- [ (meth) acryloyloxydiethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytriethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyethtetraethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxypentaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyhexaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyheptaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxyoctaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxynonaethoxy ] phenyl } propane, 2, 2-bis {4- [ (meth) acryloyloxydiethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydecylethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydodecoxyethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydridecyloxyethyl ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxytetradecyloxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydentadecaethoxy ] phenyl } propane, 2-bis {4- [ (meth) acryloyloxydetaxethoxy ] phenyl } propane and the like. The number of ethylene oxide groups in 1 molecule of the 2, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane is preferably 4 to 20, more preferably 8 to 15. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylate compound having a urethane bond in the molecule include: an addition reaction product of a (meth) acrylic monomer having an OH group at the β -position and a diisocyanate compound (isophorone diisocyanate, 2, 6-toluene diisocyanate, 2, 4-toluene diisocyanate, 1, 6-hexamethylene diisocyanate, etc.), tris [ (meth) acryloxytetraethylene glycol isocyanate ] hexamethylene isocyanurate, EO-modified urethane di (meth) acrylate, PO-modified urethane di (meth) acrylate, EO, PO-modified urethane di (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the nonylphenoxy polyethyleneoxy acrylate include: nonylphenoxy tetraethoxy acrylate, nonylphenoxy pentaethyleneoxy acrylate, nonylphenoxy hexaethyleneoxy acrylate, nonylphenoxy heptaethyleneoxy acrylate, nonylphenoxy octaethyleneoxy acrylate, nonylphenoxy nonaethyleneoxy acrylate, nonylphenoxy decaethyleneoxy acrylate, nonylphenoxy undecenyloxy acrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the phthalic acid-based compound include: gamma-chloro-beta-hydroxypropyl-beta '- (meth) acryloyloxyethylphthalate, beta-hydroxyalkyl-beta' - (meth) acryloyloxyalkylphthalate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the alkyl (meth) acrylate include: 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, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, pentyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, propylene glycol polypropylene ether di (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, ethoxylated polytetrahydrofuranediol di (meth) acrylate, ethoxylated polypropylene glycol di (meth) acrylate, and the like. Among them, methyl (meth) acrylate, ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexaacrylate are preferable. These compounds may be used alone or in combination of two or more.
The compound having an ethylenically unsaturated double bond is preferably a bisphenol a (meth) acrylate compound or a (meth) acrylate compound having a urethane bond in the molecule, from the viewpoint of improving adhesiveness. From the viewpoint that sensitivity and resolution can be improved, bisphenol a (meth) acrylate compounds are preferable. As commercially available products of bisphenol a-based (meth) acrylate compounds, 2-bis {4- [ (meth) acryloyloxypolyethoxy ] phenyl } propane (manufactured by shinkamura chemical industries, ltd., BPE-200), 2-bis {4- [ (meth) acryloyloxypolypropoxy ] phenyl) propane (manufactured by shinkamura chemical industries, ltd., BPE-5000; FA-321M manufactured by Hitachi chemical Co., Ltd.), 2-bis {4- [ (meth) acryloyloxypolybutoxy ] phenyl } propane (New Zhongmura chemical Co., Ltd., BPE-1300), and the like.
The content of the compound having an ethylenically unsaturated double bond is 25 to 99 parts by weight, preferably 55 to 90 parts by weight, in 100 parts by weight of the photosensitive resin composition.
Hydrogen donor
The photosensitive resin composition of the present invention further comprises a hydrogen donor. The double imidazole compounds are cracked after illumination, the generated single imidazole free matrix has larger volume, the steric effect causes smaller activity, and the monomer polymerization is difficult to initiate independently, and if the double imidazole compounds are matched with a hydrogen donor, the single imidazole free radical is easy to capture active hydrogen on the hydrogen donor to generate new active free radical, and further initiates the monomer polymerization.
The specific type is not particularly limited as long as the hydrogen donor has the above-described characteristics. Without limitation, suitable hydrogen donors may be amines or amine modified compounds, thiols, which have available hydrogens attached to carbons adjacent to a heteroatom. These compounds may be used alone, or in combination of two or more thereof.
Illustratively, the amine compound may be an aliphatic amine, a cycloaliphatic amine, an aromatic-aliphatic amine, a heterocyclic amine, an oligomeric amine, or a polymeric amine. They may be primary, secondary or tertiary amines, for example butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, N-phenylglycine, triethylamine, phenyl-diethanolamine, triethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, dimethylaminobenzoate, Michler's ketone (Michler ' sketone) (4,4' -bis-dimethylaminobenzophenone), and the corresponding derivatives.
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 may be disclosed in US3,844,916, EP280222, US5,482,649 or US5,734,002, which are incorporated herein by reference in their entirety.
Without limitation, preferred amines or amine-modified compounds are: EsacureA198 (bis-N, N- [ 4-dimethylaminobenzoyl) oxoethen-1-yl ] -methylamine) and esacurededb (ethyl-4-dimethylaminobenzoate), both sold by lamberti s.p.a., italy, 2-ethylhexyl-4-dimethylaminobenzoate and N-phenylglycine.
The thiol compound may be primary thiol, secondary thiol and multifunctional thiol, preferably secondary thiol and multifunctional thiol. Exemplary, the thiol-based compound may be: 2-Mercaptobenzothiazole (MBO), 2-Mercaptobenzimidazole (MBI), dodecylmercaptan, 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 tetrakis (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), Trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), 1, 2-propanediol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexa (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1, 2-propanediol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), Butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), 1, 2-propanediol bis (4-mercaptoisovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), 1, 2-propanediol bis (3-mercaptovalerate), Aliphatic secondary/multifunctional thiol compounds such as diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexa (3-mercaptovalerate), and the like; examples of aromatic secondary/multifunctional thiol compounds are: di (1-mercaptoethyl) phthalate, di (2-mercaptopropyl) phthalate, di (3-mercaptobutyl) phthalate, di (3-mercaptoisobutyl) phthalate, and the like. Of these, ethylene glycol bis (3-mercaptobutyrate), 1, 2-propylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1, 2-propylene glycol bis (2-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptopropionate) are particularly suitable.
The content of the hydrogen donor is 0.01 to 15 parts by weight, preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, in 100 parts by weight of the photosensitive resin composition, and the weight ratio of the hydrogen donor to the HABI type hybrid photoinitiator represented by the general formula (I) is preferably 1:20 to 1: 3.
Other optional photoinitiators and/or sensitizers
Optionally, the photosensitive resin composition of the present invention may further contain other photoinitiators and/or sensitizers to more flexibly adjust the sensitivity of the photosensitive resin composition by 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.
Exemplary bisimidazoles include: 2,2' -bis (o-chlorophenyl) -4,4',5,5' -tetraphenyl-diimidazole, 2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5' -diphenyl-1, 1 ' -diimidazole, 2', 5-tris (2-fluorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5' -diphenyl-diimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-diimidazole, 2' -bis (2-fluorophenyl) -4- (o-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4',5' -diphenyl-diimidazole, 2' -bis (2-fluorophenyl) -4,4',5,5' -tetraphenyl-diimidazole, 2' -bis (2-methoxyphenyl) -4,4',5,5' -tetraphenyl-diimidazole, 2' -bis (2-chloro-5-nitrophenyl) -4,4' -bis (3, 4-dimethoxyphenyl) -5,5' -bis (o-chlorophenyl) -diimidazole, 2' -bis (2-chloro-5-nitrophenyl) -4- (3, 4-dimethoxyphenyl) -5- (o-chlorophenyl) -4',5' -diphenyl-diimidazole, 2,2 '-bis (2, 4-dichlorophenyl) -4,4' -bis (3, 4-dimethoxyphenyl) -5,5 '-bis (o-chlorophenyl) -diimidazole, 2- (2, 4-dichlorophenyl) -4- (3, 4-dimethoxyphenyl) -2', 5-bis (o-chlorophenyl) -4',5' -diphenyl-diimidazole, 2- (2, 4-dichlorophenyl) -2 '- (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-diimidazole, 2' -bis (2, 4-dichlorophenyl) -4,4',5,5' -tetraphenyl-diimidazole and the like. These bisimidazoles may be used alone or in combination of two or more.
Exemplary pyrazolines include: 1-phenyl-3- (4-tert-butylstyryl) -5- (4-tert-butylphenyl) pyrazoline, 1-phenyl-3-biphenyl-5- (4-tert-butylphenyl) pyrazoline, ethoxylated (9) trimethylolpropane pyrazoline ester, ethoxylated (10) bisphenol A pyrazoline ester, and the like. These pyrazolines may be used alone or in combination of two or more.
Exemplary aromatic ketones include: acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4 '-methylbenzophenone sulfide, 4-benzoyl-4' -ethyldiphenyl sulfide, 4-benzoyl-4 '-propyldiphenyl sulfide, 4' -bis (diethylamino) benzophenone, 4-p-tolylmercapto benzophenone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone, 4 '-bis (dimethylamino) benzophenone, 4' -bis (methyl, ethylamino) benzophenone, acetophenone dimethyl ketal, benzophenone derivatives, and mixtures thereof, Benzil dimethyl ketal,. alpha. -dimethylbenzyl ketal,. alpha. -diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylbenzophenone, 2-hydroxy-2-methyl-1-p-hydroxyethyl etherylphenylacetone, 2-methyl-1- (4-methylmercaptophenyl) -2-morpholine-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) 1-butanone, phenylbis (2,4, 6-trimethylbenzoyl) oxyphosphine, 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2-hydroxy-1- {3- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,1, 3-trimethyl-inden-5-yl } -2-methyl acetone; and 2-hydroxy-1- {1- [4- (2-hydroxy-2-methyl-propionyl) -phenyl ] -1,3, 3-trimethyl-inden-5-yl } -2-methyl-propanone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) one, and the like. These aromatic ketone compounds may be used alone or in combination of two or more.
Exemplary anthraquinones include: 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone-9, 10-diethyl ester, 1,2, 3-trimethylanthracene-9, 10-dioctyl ester, 2-ethylanthrane-9, 10-bis (4-chlorobutyric acid methyl ester), 2- (3- ((3-ethyloxetan-3-yl) methoxy) -3-oxopropyl) anthracene-9, 10-diethyl ester, 9, 10-dibutoxyanthracene, 9, 10-diethoxy-2-ethylanthracene, 9, 10-bis (3-chloropropoxy) anthracene, 9, 10-bis (2-hydroxyethylmercapto) anthracene, 1-chloroanthraquinone, 2-methylanthraquinone, 2, 3-dimethylanthraquinone, 2-ethylanthraquinone-, 9, 10-bis (3-hydroxy-1-propylmercapto) anthracene and the like. These anthraquinone compounds may be used alone or in combination of two or more.
Exemplary 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.
Exemplary oxime ester compounds include: 1- (4-thiophenylphenyl) -n-octane-1, 2-dione-2-oxime benzoate, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) -ethane-1-one-oxime acetate, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) -butane-1-one-oxime acetate, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) -propane-1-one-oxime acetate, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) -1-cyclohexyl-methane -1-ketone-oxime acetate, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) -3-cyclopentyl-propane-1-one-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime benzoate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime benzoate, 1- (4-benzoyldiphenyl sulfide) - (3-cyclopentylacetone) -1-oxime acetate, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (4-benzoyldiphenyl sulfide) - (3-cyclopentylacetone) -1-oxime cyclohexanecarboxylate, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentyl) -propane-1, 2-dione-2-o-methylbenzoic acid oxime ester, 1- (4-phenylthiophenyl) - (3-cyclopentyl) -propane-1, 2-dione-2-cyclohexanecarboxylic acid oxime ester, 1- (4-thenoyl-diphenylsulfide-4' -yl) -3-cyclopentyl-propane-1-one-acetic acid oxime ester, 1- (4-benzoyldiphenylsulfide) - (3-cyclopentyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-nitro-9-ethylcarbazol-3-yl) -3-cyclohexyl-propane-1-one-acetic acid oxime ester, and salts thereof, 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (6-furfurylcarbazol-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime acetate, 1, 4-diphenylpropane-1, 3-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, 1- (6-furoyl-9-ethylcarbazol-3-yl) - (3-cyclohexylacetone) -1-oxime acetate, 1- (4-phenylthiophenyl) - (3-cyclohexyl) -propane-1, 2-dione-3-oxime benzoate, 1- (6-thenoyl-9-ethylcarbazol-3-yl) - (3-cyclohexyl) -propane-1, 2-dione-2-oxime acetate, oxime, 2- ((benzoyloxy) imino) -1-phenylpropan-1-one, 1-phenyl-1, 2-propanedione-2- (oxoacetyl) oxime, 1- (4-phenylthiophenyl) -2- (2-methylphenyl) -ethane-1, 2-dione-2-oxime acetate, 1- (9, 9-dibutyl-7-nitrofluoren-2-yl) -3-cyclohexyl-propan-1-one-oxime acetate, 1- (4- (4- (thiophene-2-formyl) phenylthiophenyl) -3-cyclopentylpropane-1, 2-dione-2-oxime acetate, and pharmaceutically acceptable salts thereof, 1- (9, 9-dibutyl-2-yl) -3-cyclohexylpropylpropane-1, 2-dione-2-oxime acetate, 1- (6- (2- (benzoyloxyimino) -3-cyclohexylpropyl-9-ethylcarbazol-3-yl) octane-1, 2-dione-2-oxime benzoate, 1- (7-nitro-9, 9-diallylfluoren-2-yl) -1- (2-methylphenyl) methanone-oxime acetate, 1- (6- (2-methylbenzoyl) -9-ethylcarbazol-3-yl) -3-cyclopentyl-propane-1-one-oxime benzoate, and pharmaceutically acceptable salts thereof, 1- (7- (2-methylbenzoyl) -9, 9-dibutylfluoren-2-yl) -3-cyclohexylpropane-1, 2-dione-2-oxime acetate, 1- (6- (furan-2-formyl) -9-ethylcarbazol-3-yl) -3-cyclohexylpropane-1, 2-dione-2-carbethoxyoxime ester, and the like. These oxime ester compounds may be used alone or in combination of two or more.
Exemplary triazines include: 2- (4-ethylbiphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4-methyleneoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 1,1,1,3,3, 3-hexafluoroisopropyl-3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoate, ethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, methyl-ethyl-2, 4-bis (trichloromethyl) -s-triazin, 2-ethoxyethyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, cyclohexyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } acetate, 3- { chloro-4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, 3- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanamide, benzyl-2- {4- [2, 4-bis (trichloromethyl) -s-triazin-6-yl ] phenylthio } propanoic acid, and the like, 2, 4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2, 4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1, 3-butadienyl-s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, and the like. These triazine compounds may be used alone or in combination of two or more.
Exemplary triphenylamine-based compounds include: n, N-bis- [4- (2-styryl-1-yl) -phenyl ] -N, N-bis (2-ethyl-6-methylphenyl) -1, 1-bisphenyl-4, 4-diamine, N-bis- [4- (2-styryl-1-yl) -4' -methylphenyl ] -N, N-bis (2-ethyl-6-methylphenyl) -1, 1-bisphenyl-4, 4-diamine, and the like. These triphenylamine compounds may be used alone or in combination of two or more.
Exemplary coumarins include: 3,3 '-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-diethylaminocoumarin, 3' -carbonylbis (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 the like. These coumarins may be used alone or in combination of two or more.
Exemplary 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.
Exemplary acridine compounds include: 9-phenylacridine, 9-p-methylphenylacridine, 9-m-methylphenylacridine, 9-o-chlorophenylacridine, 9-o-fluorophenylacridine, [4- (9-acridinyl) phenoxy ] acetate of 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol ether cyclohexane ether (i.e., PAD107, available from Kyowa Strong Electron 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-acridinopentane), 1, 3-bis (9-acridine) propane, and the like. These acridine compounds may be used alone or in combination of two or more.
Preferably, the content of the other photoinitiator and/or sensitizer is not more than 8 parts by weight in 100 parts by weight of the photosensitive resin composition.
Other optional adjuvants
In addition to the above components, the photosensitive resin composition of the present invention may optionally contain other additives in appropriate amounts as required. Illustratively, the auxiliary may include at least one of an organic solvent, a dye, a pigment, a photo developer, a filler, a plasticizer, a stabilizer, a coating auxiliary, a peeling promoter, and the like.
The organic solvent may be any solvent as long as it can dissolve the above components, and may be exemplified by glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, chlorine-containing solvents, and the like, and is preferably selected in consideration of the solubility of the colorant and the alkali-soluble polymer, coatability, safety, and the like. Preferably, 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 glycol mono-t-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 acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, n-butyl acetate, Ethyl 3-ethoxypropionate (EEP), methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5, 5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2, 6-dimethyl-4-heptanone), N-methylpyrrolidone (4-methylaminolactam or NMP), methanol, ethanol, isopropanol, N-propanol, isobutanol, N-butanol, and the like. These solvents may be used alone, or two or more thereof may be used in combination.
As the dye, pigment and light developer, there may be exemplified: 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 systems, auramine base, parafuchsin, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite green, chrysin green, basic blue 20, brilliant green, eosin, ethyl violet, dittanium sodium salt B, methyl green, phenolphthalein, alizarin red S, thymolphthalein, methyl violet 2B, quinadine red, rhodol sodium agar, mirderlein, thymolsulfonphthalein, xylenol blue, methyl orange, tangerine IV, diphenylene flow carbazone, 2, 7-dichlorofluorescein, carmellose red, congo red, wool violet 4B, alpha-naphthylred, phenacetin, methyl violet, victoria pure blue, rhodamine 6G, BOH, Organic pigments such as diphenylamine, dibenzylaniline, triphenylamine, diethylaniline, di-p-phenylenediamine, p-toluidine, benzotriazole, tolyltriazole, 4' -diaminobenzidine, o-chloroaniline, white crystal violet, white malachite green, white aniline, white methyl violet, azo pigments and inorganic pigments such as titanium dioxide. In view of good contrast, tris (4-dimethylaminophenyl) methane (i.e. leuco crystal violet, LCV) is preferably used. These dyes, pigments and optical developers may be used singly or in combination of two or more.
As the filler, exemplarily, there may be: fillers (not including the inorganic pigments) such as silica, alumina, talc, calcium carbonate, and barium sulfate. The filler may be used alone or in combination of two or more.
As the plasticizer, for example, there may be: phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate and diallyl phthalate, ethylene glycol esters such as triethylene glycol diacetate and tetraethylene glycol diacetate, sulfonamides such as p-toluenesulfonamide, benzenesulfonamide and n-butylbenzenesulfonamide, triphenyl phosphate, trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, trixylyl phosphate, 2-naphthyl diphenyl phosphate, cresyl di-2, 6-xylyl phosphate, aromatic condensed phosphate, tris (chloropropyl) phosphate, tris (tribromoneopentyl) phosphate, halogen-containing condensed phosphate, triethylene glycol dioctoate, triethylene glycol di (2-ethylhexanoate), tetraethylene glycol diheptanoate, diethyl sebacate, diethylene glycol monobutyl phthalate, neopentyl glycol monobutyl ether, neopentyl glycol ether, diphenyl ether, Dibutyl suberate, tris (2-ethyl) phosphate, Brij30 [ C ]12H25(OCH2CH2)4OH]And Brij35[ C ]12H25(OCH2CH2)20OH]And the like. The plasticizer may be used alone or in combination of two or more.
As the stabilizer, exemplarily, there may 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 hydroquinones and quinones, t-butyl catechol, 1,2, 3-benzenetrisol, copper resinate, naphthylamine, β -naphthol, cuprous chloride, 2, 6-di-t-butyl-p-cresol, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone, chloranil and the like. The stabilizer may be used alone or in combination of two or more.
The coating auxiliary may be, in view of safety and versatility: acetone, methanol, methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methylene chloride, and the like. The coating aids may be used singly or in combination.
Examples of the peeling accelerator include: benzene sulfonic acid, toluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid, alkyl benzene sulfonic acid such as methyl, propyl, heptyl, octyl, decyl, dodecyl and the like. The peeling accelerator may be used alone or in combination of two or more.
Preferably, the total content of the auxiliaries is not more than 10 parts by weight in 100 parts by weight of the photosensitive resin composition.
< UVLED photocuring application >
In the application of the invention, the wavelength of the LED light source is within the range of 355 and 420nm, and can be 365nm, 385nm, 395nm, 405nm and the like.
The photosensitive resin composition of the present invention can be used as an ink and a coating composition for coating a metal surface, a wood surface, a paper surface, a plastic surface, and the like. For particular applications, the ink or coating composition may be applied using flexographic, offset, gravure or inkjet printing methods and then radiation cured. The above-described photosensitive resin composition of the present invention can be cured in the presence of oxygen, thereby obviating the need to provide an inert oxygen-free environment to prevent oxygen inhibition during curing.
Drawings
FIG. 1 is a high performance liquid chromatogram of product A1.
FIG. 2 is a structural spectrum of BCIM obtained by single crystal diffraction.
Detailed Description
The present invention is described in further detail with reference to specific examples, which should not be construed as limiting the scope of the invention.
Preparation of HABI type Mixed photoinitiator
1.1 preparation of HABI-based Mixed photoinitiator A1
Under the protection of nitrogen, 31.8g of 2- (o-chlorophenyl) -4, 5-diphenyl-Imidazole (INC), 51.3g of 2, 5-bis (o-chlorophenyl) -4- (4, 5-dimethoxyphenyl) -imidazole (TAI), 106g of 30% caustic soda liquid, 4.0g of tetrabutylammonium bromide and 300g of toluene are put into a 1L four-neck flask, heated and stirred, 130g of sodium hypochlorite (11% concentration) is dropwise added at 60-65 ℃, the reaction is kept warm after the dropwise addition is finished, samples are taken and are subjected to central control by HPLC until INC and TAI are both less than 1%, the reaction is completed, and the heat preservation is finished.
After completion of the incubation reaction, the reaction mixture was washed four times with 100g of pure water, and then the aqueous layer was extracted once with 20g of toluene, and the organic layer was distilled under reduced pressure. And adding 70g of methanol into the material obtained by distillation, heating and stirring until the solution is clear, then dropwise adding the clear solution into a recrystallization solution prepared from 30g of methanol and 50g of pure water, and leaching, draining and drying the material after the dropwise adding is finished to obtain 79.1g of the product A1.
FIG. 1 is a high performance liquid chromatogram of product A1. The analysis result showed that the total peak content of the products at the four linking sites of 2-1 ', 2-3', 2 '-1 and 2' -3 was 92.5%.
The product A1 is a mixture of two different mono-imidazoles (i.e., INC, TAI) coupled to each other and to each other, including BCIM, TCTM and TCDM. In order to accurately verify the structural composition of the product, verification analysis is respectively carried out on the components BCIM, TCTM and TCDM.
Pure BCIM, TCTM and TCDM are respectively obtained by means of single imidazole self-coupling, column chromatography, chromatographic separation and the like, and the structure is respectively confirmed.
BCIM has only one peak in the liquid phase, but two peak shapes are obtained by single crystal diffraction, see figure 2. The structural characteristics can be determined by combining the structural characteristics, the main product of the coupling of two single imidazoles is a mixture of N containing hydrogen on one imidazole and C at the 2-position on the other imidazole, thereby indicating that the structure of BCIM is the two connection positions of 2 '-1 and 2' -3 in the invention.
The imidazole for synthesizing BCIM is INC, belongs to symmetrical imidazole, so that 2 '-1 and 2' -3 obtained by coupling have similar polarity, and the liquid phase is difficult to separate. And because of the structural symmetry of INC, 2 '-1 and 2-1' in the structure of the product obtained by coupling the INC are the same, and 2 '-3 and 2-3' are also the same, so the main structure of BCIM is the product of two connection sites of 2 '-1 and 2' -3, the structural formula is shown as follows, and is BCIM1 respectively: 2,2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -diimidazole and BCIM 2: 2,2 '-bis (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-2', 3-diimidazole;
Figure RE-GDA0002084914610000271
similarly, the pure TCTM obtained by separation was analyzed, the main structure was four junction products, and LCMS was performed to confirm the structure. The mass spectrometry obtains 849 and 850 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 848, the product is matched with T +1 and T +2, and the four products are proved to be similar in structure and identical in molecular weight. The mono-imidazole TAI for the synthesis of TCTM belongs to the asymmetric mono-imidazole, so there are two configurations for TAI, TAI1 and TAI2, as shown below:
Figure RE-GDA0002084914610000272
TCTM is synthesized by asymmetric single imidazole coupling, eight main structures connected by 1-2 and 2-3 connecting positions exist theoretically, but 2 '-1 and 2-1' in the structures are the same, and 2 '-3 and 2-3' in the structures are also the same for self-coupled single imidazole, so that for TCTM, four main structures connected by 1-2 and 2-3 connecting positions exist actually, and the compositions are respectively:
TCTM 1:2, 2',5, 5' -tetrakis (o-chlorophenyl) -4,4 '-bis (3, 4-dimethoxyphenyl) -2', 3-diimidazole, TCTM 2: 2,2', 4,5' -tetrakis (o-chlorophenyl) -4', 5-bis (3, 4-dimethoxyphenyl) -1, 2' -diimidazole, TCTM 3: 2,2',5, 5' -tetrakis (o-chlorophenyl) -4,4 '-bis (3, 4-dimethoxyphenyl) -1, 2' -diimidazole, TCTM 4: 2,2', 4,5' -tetrakis (o-chlorophenyl) -4', 5-bis (3, 4-dimethoxyphenyl) -2', 3-diimidazole, the structure of which is shown below:
Figure RE-GDA0002084914610000281
Figure RE-GDA0002084914610000291
the TCDM is formed by coupling INC and TAI in pairs, the main structure of the separated pure TCDM in a liquid phase is a product with four connecting positions, and the LCMS is carried out on the product with the four connecting positions to confirm the structure. The mass spectrometry obtains 755 and 756 molecular fragment peaks by means of instrument attached software, the molecular weight of the product is 754, and the product is matched with T +1 and T +2, and the four products are proved to be similar in structure and identical in molecular weight. The TCDM is formed by pairwise connection of symmetrical imidazole INC and asymmetrical imidazole TAI, and has four main structures connected by connecting positions 1-2 and 2-3, and the TCDM respectively comprises the following components:
TCDM 1:2, 2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1, 2' -diimidazole, TCDM 2: 2,2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-2', 3-diimidazole, TCDM 3: 2,2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-2, 3' -diimidazole, TCDM 4: 2,2', 5-tris (o-chlorophenyl) -4- (3, 4-dimethoxyphenyl) -4',5 '-diphenyl-1', 2-diimidazole having the following structural formula:
Figure RE-GDA0002084914610000292
Figure RE-GDA0002084914610000301
the analysis of the above experiments confirms that the product A1 is formed by combining BCIM (BCIM1, BCIM2), TCTM (TCTM1, TCTM2, TCTM3, TCTM4) and TCDM (TCDM1, TCDM2, TCDM3 and TCDM4), wherein the content of the bisimidazole compound formed by four connecting positions of 2-1 ', 2-3', 2 '-1 and 2' -3 in A1 is 92.5%.
1.2 preparation of A2-A8
Referring to the preparation method of A1, A2-A8 were prepared separately, and the product cases are shown in Table 1 below.
TABLE 1
Figure RE-GDA0002084914610000311
The molar extinction coefficient testing method comprises the following steps:
absorbance of the test product at 0.01% acetonitrile, calculated as ═ a/Cb, where C is the relative concentration (mol/L) and a is the absorbanceThe light intensity is the molar absorption coefficient (L/mol. cm), and b is the cell thickness (cm). In the test conditions of the present invention, C is 10-4mol/L, b is 1 cm.
2. Photosensibility test
2.1 preparation of samples to be tested
Ebecryl605 and Ebecryl350 (cytec industries inc.) were mixed in an amount of 99.5:0.5 parts by weight, and 3 parts by weight of a photoinitiator and 1 part by weight of hydrogen donor esacruededb (sold by sapphire ltd) were added to prepare a composition to be tested.
In addition to the photoinitiators in Table 1 above, two photoinitiators commonly used in the art, i.e., Isopropylthioxanthone (ITX) and triphenylphosphine oxide (TPO), were selected for comparison.
2.2 test methods
A sample of the composition to be tested was placed in the sample holder of FT-IR (FT-IR430-Jasco) and exposed to an LED light source (365, 385, 395 or 405nm) at an angle of 30 DEG at a distance of 65 mm from the sample.
In the photopolymerization, IR spectra were collected by Fourier Infrared spectrometer and 1408cm of the double bond assigned to the acrylic acid was determined by IR software-1And 810cm-1The peak area is the peak area before and after the light irradiation. The reduction (%) of the peak area was calculated to quantify the degree of polymerization and, hence, the efficiency of the photoinitiator. The larger the decrease (%) in peak area, the higher the double bond conversion per unit time, and the better the sensitivity of the initiator.
2.3 test results
The test results are shown in the following table, and are expressed as the degree of decrease (%) in the 3S internal peak area.
TABLE 2
Figure RE-GDA0002084914610000331
A9：BCIM
Figure RE-GDA0002084914610000332
A10：HABI104
Figure RE-GDA0002084914610000341
As can be seen from the above table, the HABI-based hybrid photoinitiators (a1, a2, A3) of the present invention have similar sensitivity to TPO and ITX, the comparative examples (a4, a) have lower solubility and affect the use in the formulation, and the comparative examples (a6, a7, A8) have lower sensitivity than the examples, but do not achieve the use effect of TPO and ITX; the comparative examples (A9, A10) have low sensitivity under UVLED and are difficult to apply because the substitution position does not conform to the substitution rules of the present invention.
The results show that the HABI-based hybrid photoinitiator of the present invention has photosensitivity comparable to that of the prior art in a photosensitive resin composition when an LED is used as a light source.
3. Film Forming Property test
3.1 preparation of samples to be tested
Taking A1, A2, A3 and A9 as examples, samples were prepared according to the following formulations and evaluated for film forming properties:
free radical polymerization monomer TMPTA 94 weight parts
Photoinitiator 5 parts by weight
1 part by weight of N-PG (hydrogen donor).
Commercial TPO and ITX photoinitiators were used for comparison.
3.2 test methods
Uniformly stirring a composition sample to be detected in a dark place, sampling on a PET substrate, coating by a 25# wire rod to form a coating film with the thickness of 25 mu m, and then using an LED light source (the radiation wavelength is 385nm, and the exposure is 240 mj/cm)2) And (4) carrying out radiation curing on the coating film.
The cure of each formulation was examined both superficially and basely. The surface curing condition is evaluated by referring to a finger touch method in a paint film drying time test standard GB/T1728-1979, namely, the coating is touched by fingers to ensure that the surface is smooth and the surface is completely cured without hands; the bottom curing condition is measured by adopting a finger-scratching method, namely, the coating is scratched by a fingernail lightly, and the phenomenon of no falling or bottom exposure indicates that the bottom layer is completely cured.
The surface morphology of the cured film was observed by naked eyes and the cured film was evaluated for lack of irritating odor by a fan-smelling method. The flatter the surface, the better the compatibility with the monomer; the lower the odor, the less volatile is indicated.
Yellowing test: the exposed cured film test panel was placed in a fluorescent UV-aging machine at 120 + -5 deg.C under 0.68W/m2 with drying (no condensation) using a UVA (340) lamp as the light source, and the continuous illumination was maintained for 168 hours throughout. And (4) taking out after the illumination is finished, comparing the sample with a test plate after the initial TPO exposure, and measuring the color change by using a color difference meter, wherein the color change value unit is delta E. The smaller the measured value, the closer the color.
3.3 test results
Specific test results are shown in table 3.
TABLE 3
Figure RE-GDA0002084914610000361
From the above tests, it can be seen that the HABI-based hybrid photoinitiator of the present invention has superior surface dry effect, lower odor and less yellowing, and is safer to use, compared to both a9 and prior art TPO and ITX.

Claims (15)

  1. Use of a HABI based hybrid photoinitiator in uv led photocuring, characterized in that a photosensitive resin composition comprising the following components:
    (a)0.1 to 20 weight portions of HABI mixed photoinitiator which has the structure shown in the general formula (I) and contains 2 to 1 ', 2 to 3', 2 '-1 and 2' -3 double imidazole compounds of four connection sites, wherein the total mass percentage content of the four double imidazole compounds of the connection sites in the HABI mixed photoinitiator is more than 92 percent,
    Figure FDA0002011680810000011
    wherein Ar is1、Ar2、Ar3、Ar4、Ar5、Ar6May be the same or different and each independently represents a substituted or unsubstituted aryl group;
    wherein at least one ortho-position substituent on the 2-position or 2' -position aryl is an electron-withdrawing substituent, and at least one substituent on the 4-position aryl or 4' -position aryl or 5' -position aryl is provided with an electron-donating substituent;
    the molar extinction coefficient of the HABI mixed photoinitiator at 355-420nm is more than 6000 and less than 13000;
    (b)25 to 99 parts by weight of at least one compound having an ethylenically unsaturated double bond;
    (c)0.01-15 parts by weight of hydrogen donor, wherein the weight ratio of the hydrogen donor to the HABI mixed photoinitiator shown in the general formula (I) is 1:20-1: 1.
  2. 2. Use according to claim 1, characterized in that: in the general formula (I), the aryl group is a phenyl group.
  3. 3. Use according to claim 1, characterized in that: in the general formula (I), the electron-withdrawing substituent on the aryl is selected from halogen, nitro, cyano and amino, and the electron-donating substituent on the aryl is selected from methoxy and C3-C10Branched alkyl or alkenyl groups of (a).
  4. 4. Use according to claim 1 or 2, characterized in that: in the general formula (I), Ar1、Ar2、Ar3、Ar4、Ar5、Ar6At least one is an aryl group having a halogen substituent; preferably, the halogen substituent is chlorine.
  5. 5. Use according to claim 1, characterized in that: as HABI mixed photoinitiator, the total mass percentage content of the bisimidazole compound satisfying four connecting positions of 2-1 ', 2-3', 2 '-1 and 2' -3 of the structure shown in the general formula (I) is more than 95%.
  6. 6. Use according to claim 1 or 5, characterized in that: the HABI mixed photoinitiator is composed of a bisimidazole compound with four connecting positions of 2-1 ', 2-3', 2 '-1 and 2' -3 which satisfy the structure shown in a general formula (I).
  7. 7. Use according to claim 1, characterized in that: the compound having an ethylenically unsaturated double bond is selected from a compound obtained by reacting an alpha, beta-unsaturated carboxylic acid with a polyhydric alcohol, a bisphenol A (meth) acrylate compound, alpha, a compound obtained by reacting a β -unsaturated carboxylic acid with a glycidyl group-containing compound, a (meth) acrylate compound having an amino ester bond in the molecule, nonylphenoxy polyethyleneoxy acrylate, γ -chloro- β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxyethyl- β ' - (meth) acryloyloxyethyl-phthalate, β -hydroxypropyl- β ' - (meth) acryloyloxyethyl-phthalate, a phthalic compound, and an alkyl (meth) acrylate.
  8. 8. Use according to claim 1 or 7, characterized in that: the compound having an ethylenically unsaturated double bond is selected from bisphenol A (meth) acrylate compounds and (meth) acrylate compounds having an urethane bond in the molecule.
  9. 9. Use according to claim 1, characterized in that: the hydrogen donor is an amine or amine modified compound, a thiol compound, having an available hydrogen attached to a carbon adjacent to a heteroatom.
  10. 10. Use according to claim 9, characterized in that: the amine or amine modified compound is selected from at least one of EsacureA198, EsacureEDB, 2-ethylhexyl-4-dimethylaminobenzoate and N-phenylglycine.
  11. 11. Use according to claim 9, characterized in that: the thiol compound is at least one selected from ethylene glycol bis (3-mercaptobutyrate), 1, 2-propylene glycol bis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), 1, 2-propylene glycol bis (2-mercaptoisobutyrate), and pentaerythritol tetrakis (3-mercaptopropionate).
  12. 12. Use according to claim 1, characterized in that: the weight ratio of the hydrogen donor to the HABI mixed photoinitiator shown in the general formula (I) is 1:20-1: 3.
  13. 13. Use according to claim 1, characterized in that: the photosensitive resin composition may further contain other photoinitiator and/or sensitizer.
  14. 14. Use according to claim 1, characterized in that: in the application, the wavelength of the UVLED light source is in the range of 355 and 420nm, including 365nm, 385nm, 395nm and 405 nm.
  15. 15. Use according to claim 1, characterized in that: the photosensitive resin composition is used as an ink and a coating composition.
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