CN111018763A - Bis-triphenyl sulfonium salt compound and application thereof - Google Patents
Bis-triphenyl sulfonium salt compound and application thereof Download PDFInfo
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Abstract
The invention discloses a novel bis-triphenyl sulfonium salt compound which has a structure shown as a general formula (I), wherein R is1Represents an electron withdrawing group, R2Represents an amplifying group. The compound has excellent solubility and photosensitivity, and can be used asIs a good substitute for resist acid generators and photoinitiators for cationic polymerization.
Description
Technical Field
The invention belongs to the technical field of radiation curing, and particularly relates to a bis-triphenylsulfonium salt compound and application thereof.
Background
Compared with a free radical type photo-curing system, the cationic photo-curing system has the advantages of small oxygen inhibition, small volume shrinkage during curing, wider selection of resin types and the like, and is widely used for manufacturing electronic parts and semiconductor components. Triphenylsulfonium salts have high photosensitivity to exposure light sources such as KrF or ArF excimer laser, and are generally used as photoacid generators/photoinitiators for chemically amplified resists for mass production of semiconductor devices. However, the triphenylsulfonium salt has a symmetrical cationic structure and high crystallinity, and is poor in solubility in a photocurable monomer and a conventional organic solvent, so that the amount of addition is limited, and problems such as uneven dispersion in a composition and precipitation during use are likely to occur.
To improve the solubility, JP2005091976A and JP2002193925A introduce a substituent group such as an alkyl group or a fluoroalkyl group at the para-position of the benzene ring group, and WO2005037778A introduces an alkyl group at the meta-position of the benzene ring group, and they have improved solubility in a solvent but greatly reduced photosensitive activity as compared with those having no substituent group. TW201444790A introduced an electron-withdrawing group in the meta-position of the benzene ring group, which was able to maintain the photosensitivity at the same level while increasing the solubility compared to the unsubstituted one.
There is a continuing technical and market need to optimize the structure of triphenylsulfonium salts to obtain alternatives with better application properties.
Disclosure of Invention
Aiming at the demands of application markets, the invention aims to provide a novel bis-triphenylsulfonium salt compound which has very excellent solubility and photosensitive activity and can be used as a high-quality substitute for a resist acid generator and a photoinitiator for cationic polymerization through structural improvement on the basis of the prior art.
Specifically, the bis-triphenylsulfonium salt compound of the invention has a structure shown as a general formula (I):
wherein the content of the first and second substances,
R1represents an electron withdrawing group;
R2represents an amplifying group;
R3each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R3The groups may be linked to each other to form a ring; n represents an integer of 0 to 5;
R4each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R4The groups may be linked to each other to form a ring; m represents an integer of 0 to 4;
R5each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R5The groups may be linked to each other to form a ring; p represents an integer of 0 to 4;
a and M each independently represent a linking group;
X-denotes a non-nucleophilic anion.
Without being bound by any theory known, applications show that by designing the bis-triphenylsulfonium salt structure and arranging an electron-withdrawing group and an amplifying group at the meta-position and the para-position of the benzene ring group of the bis-triphenylsulfonium salt structure respectively, the bis-triphenylsulfonium salt structure can have obviously improved solubility and photosensitive activity compared with unsubstituted triphenylsulfonium salt, and also has obvious advantages in performance compared with the prior improved substitutes described in the background art.
Detailed Description
The prior literature shows that the introduction of a substituent at the para position of a benzene ring group is beneficial to improving the solubility of the triphenyl sulfonium salt, but can generate adverse effect on the photosensitive activity. However, applicants have found that solubility and photoactivity are compatible when a para-substituent selected from a specific range is combined with a meta-electron withdrawing group.
The variable groups in the structure of formula (I) are described in more detail below.
It should be noted that, in the specification of the present application, C1-CxIn addition to 1 and x, all integer values having a carbon number between 1 and x are included, e.g., C1-C8Alkyl of (2) includes C1、C2、C3、C4、C5、C6、C7And C8All alkyl groups of (1) straight-chain or branched. Without being bound by theory, the meaning of which is not expressly set forth in the specification, but which is unambiguously and unambiguously determinable by a person skilled in the art, it being understood that the individual values included therein can serve as a basis for further modifications/limitations.
Variable group
(1)R1Electron withdrawing groups
It is believed that the introduction of an electron-withdrawing group at the benzene ring meta-position can effectively improve the solubility of the sulfonium salt, and meanwhile, the negative influence on the photosensitive activity is not generated.
As suitable electron withdrawing groups R1Selected from the group consisting of halogen, cyano, nitro, haloalkyl, acyl, acyloxy, sulfonyl.
Halogen may be fluorine, chlorine, bromine or iodine. From the viewpoint of environmental protection, fluorine is preferred.
Haloalkyl means an alkyl group in which at least one hydrogen atom is substituted with halogen, and the alkyl group may be a methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, or the like C1-C8Is straight-chain alkyl or is isoC such as propyl, isobutyl, sec-butyl, tert-butyl3-C8Or a branched alkyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like3-C8A cycloalkyl group of (a). When the haloalkyl group is selected from the group consisting of fluorine-substituted alkyl groups, the photosensitizing activity on the compound is favorable, more preferably C1-C4A perfluoroalkyl group of (a).
The acyl group may have
The structure shown in the specification, wherein R6Represents hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl. Preferably, R6Represents hydrogen, fluorine, chlorine, C1-C7Linear or branched alkyl of (2), C1-C7Linear or branched haloalkyl (more preferably, C)1-C7Linear or branched perfluoroalkyl group of (2), C6-C12Aryl of, or C7-C16An aralkyl group of (2).
The acyl group in the acyloxy group has the same meaning as shown in the above paragraph.
The sulfonyl group may be a methylsulfonyl group, difluoromethanesulfonyl group, trifluoromethanesulfonyl group, phenylsulfonyl group, tosyl group or the like.
In the general formula (I) of the present invention, an electron-withdrawing group R1Preference is given to halogen, cyano, nitro, haloalkyl, in particular those radicals which are preferred above.
(2)R2Amplifying group
The prior literature reports that the solubility can be improved by introducing a substituent at the para position of a benzene ring group of the triphenylsulfonium salt, but the photosensitive activity can be obviously reduced. Unexpectedly, there is an electron withdrawing group R in the meta position of the phenyl ring group1In the case of (3), an amplifying group R is introduced at the para-position2The compound can produce an amplification effect on the solubility and/or the photosensitive activity of the compound, and can not generate adverse effects on other properties while further improving the properties.
As the group capable of exhibiting an amplification action in the present invention, R2Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aralkyl.
The alkyl group is preferably an unsubstituted alkyl group, and may be a C group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, etc1-C8Is a straight-chain alkyl group or C such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like3-C8Branched alkyl groups of (a). More preferably, the alkyl group as the amplifier group is C1-C4The straight or branched alkyl group of (1) includes methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl.
The alkoxy groups are preferably unsubstituted, wherein the alkyl groups have the same meaning as indicated in the preceding paragraph.
The aralkyl group is an alkyl group terminated with an aryl group, and from the viewpoint of amplification, C terminated with a phenyl group is preferable1-C8More preferably C terminated with phenyl1-C4The linear alkyl group of (1) includes benzyl, phenethyl, phenylpropyl or phenylbutyl. Optionally, at least one hydrogen atom in the aralkyl group is substituted with a halogen (particularly fluorine).
Without being bound by the existing known theory, the combination of the amplification group and the electron-withdrawing group has a synergistic effect on the microscopic electronic structure of the triphenyl sulfonium salt, and the performance of the compound is improved. More specifically, the invention can further improve the solubility of the bis-triphenylsulfonium salt by adopting the amplification group, and simultaneously does not generate negative influence on the photosensitive activity, and even part of compounds show relatively better photosensitive activity.
(3)R3Substituent group
Optionally containing R in the structure of the general formula (I)3A substituent group provided that the photocurable application properties of the compound are not adversely affected.
Under this precondition, R is from the perspective of providing more of the same type of substitute3Each independently represents hydrogen, halogen, nitro, cyano, hydroxyl, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted arylOptionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R3The groups may be linked to each other to form a ring.
n represents R3The number of groups may be an integer of 0 to 5.
Those skilled in the art can understand that R is based on the basic theory of the organic field3The existence of the substituent group can influence the conjugated structure of the benzene ring and the overall structural characteristics of the bis-triphenylsulfonium. Without being bound by any theory, the results from this effect are often unpredictable, and depend more on the final presentation of the experiment.
Preferably, n is 0, in which case side reactions, which may occur during the subsequent photocuring process, or unknown negative effects on the effect, caused by the substituent groups, are avoided.
More preferably, n is 2 and two R on the same phenyl ring3Each represents R1And R2R of the uppermost benzene ring1And R2The bis-triphenylsulfonium salt is symmetrical up and down, namely the bis-triphenylsulfonium salt has a structure shown in the following general formula (II):
wherein each substituent group has the same meaning as described above.
Unexpectedly, when the bis-triphenylsulfonium salt contains symmetric electron-withdrawing groups and amplifying groups as shown in the above structure in the upper and lower four benzene ring groups, the compound exhibits significantly further improved solubility and photosensitizing activity as compared with the improved triphenylsulfonium salt in the prior art.
(4)R4Substituent group
Optionally containing R in the structure of the general formula (I)4A substituent group provided that the photocurable application properties of the compound are not adversely affected.
Under this precondition, R is from the perspective of providing more of the same type of substitute4Each independently represents hydrogen, halogen, nitro, cyanoA group, a hydroxyl group, an acyl group, an acyloxy group, a sulfonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, optionally, a carbon-carbon bond in the group may be interrupted by-O-, -S-, and R4The groups may be linked to each other to form a ring.
Halogen may be fluorine, chlorine, bromine or iodine. Fluorine is preferred from the viewpoint of cost and environmental performance.
The acyl group may be selected from: c2-C8Aliphatic acyl groups of (2) such as acetyl, propionyl, butyryl, valeryl, isovaleryl, hexanoyl, octanoyl, heptanoyl and the like; c7-C12And aromatic acyl groups such as benzoyl, methylbenzoyl, trimethylbenzoyl, α -phenylpropionyl, naphthoyl and the like.
The acyl group in the acyloxy group may have the same meaning as shown in the above paragraph.
The sulfonyl group may be a methylsulfonyl group, difluoromethanesulfonyl group, trifluoromethanesulfonyl group, phenylsulfonyl group, tosyl group or the like.
Alkyl groups may be substituted or unsubstituted. The alkyl group may be selected from C1-C8Linear, branched or cyclic alkyl groups of (a), for example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1, 2-dimethylbutyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. Preferably, the alkyl group is selected from C1-C4Straight or branched alkyl of, or C3-C6The cyclic alkyl group of (1). Substituents in substituted alkyl groups include (but are not limited to): halogen (fluorine, chlorine, bromine, iodine), amino, hydroxyl, and the like.
Alkoxy groups may be substituted or unsubstituted, wherein alkyl and substituent groups may have the same meaning as indicated in the preceding paragraph.
The aryl group may be substituted or unsubstituted. The aryl group may be phenyl, naphthyl, anthracenyl, pyrenyl, and the like. As substituents, there may be: c1-C4Alkyl groups such as methyl,Ethyl, propyl, butyl, etc., halogen such as fluorine, chlorine, bromine, iodine, C1-C3Such as methoxy, ethoxy, propoxy, acyl, sulfonyl, hydroxy, amino, nitro, phenyl, and the like.
Aralkyl is an alkyl group that terminates with an aryl group, which may be substituted or unsubstituted. Wherein the aryl moiety and the substituent may have the same meaning as indicated in the preceding paragraph. As the alkyl moiety therein, C is preferred1-C6The alkylene group of (1) includes methylene, ethylene and the like. Particularly preferably, aralkyl is benzyl, phenethyl or phenylpropyl, optionally with at least one hydrogen on the phenyl group being substituted by a substituent as indicated in the preceding paragraph.
In the general formula (I) of the present invention, R4Preference is given to hydrogen, nitro, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, in particular those preferred above.
m represents R4The number of groups may be an integer of 0 to 4. Preferably, m represents 0, 1 or 2, more preferably 0 or 1. When m is 1, R4Preferably in the ortho position to the side of the A group.
(5)R5Substituent group
Optionally containing R in the structure of the general formula (I)5A substituent group provided that the photocurable application properties of the compound are not adversely affected.
In terms of selection range, R5May have the same general formula as R4The substituents have the same meaning.
p represents R5The number of groups may be an integer of 0 to 4. Preferably, p represents 0, 1 or 2, more preferably 0 or 1. When p takes 1, R5Preferably in the ortho position to the side of the A group.
(6) Linking group
As the linking group of the two triphenylsulfonium structures, A represents a linking bond (i.e., a single bond),＊O*＊S＊Alkylene or alkenylene, M represents a null,
＊O＊*S*Or
A group, wherein R represents a linking site7、R8、R9Each independently represents hydrogen or C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20An alkylcycloalkyl group of (a).
Preferably, alkylene is C1-C4The straight chain alkylene group of (a), alkenylene group is-CH ═ CH-.
When M is empty, it represents that the two benzene rings are linked only through the linking group A. When M is not empty, preferably A represents a bond.
(7) Connection site
In the bis-triphenylsulfonium salt compound shown in the general formula (I), S atoms on the left and right sides are respectively connected with three benzene rings. The linking position of the S atom on the two central phenyl rings is preferably para to the group A.
(8) Non-nucleophilic anions
X-Denotes non-nucleophilic anions including (but not limited to): q-、ClO4 -、CN-、HSO4 -、NO3 -、CF3COO-、(BQ4)-、(SbQ6)-、(AsQ6)-、(PQ6)-、Al[OC(CF3)3]4 -、R10SO3 -、(R10SO2)3C-、(R10SO2)2N-、B(C6Q5)4 -、Ga(C6Q5)4 -Or [ (Rf)bPF6-b]-。
Q represents halogen, such as fluorine, chlorine, bromine, iodine, preferably fluorine.
R10Is represented by C1-C20Alkyl of (C)1-C20Perfluoroalkyl group of (A), or C6-C20The alkyl group and the perfluoroalkyl group may be any of linear, branched, or cyclic.
Rf represents an alkyl group in which 80% or more of hydrogen atoms are substituted with fluorine atoms, and the alkyl group includes: straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and the like, branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl and the like, and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. In Rf, the ratio of substitution with fluorine atoms is preferably 80% or more, more preferably 90% or more, and still more preferably 100% based on the number of moles of hydrogen atoms originally contained in the alkyl group. When the fluorine atom substitution ratio is within these ranges, the photosensitivity of the compound becomes better. Further, Rf may be exemplified by: CF (compact flash)3 -、CF3CF2 -、(CF3)2CF-、CF3CF2CF2 -、CF3CF2CF2CF2 -、(CF3)2CFCF2 -、CF3CF2(CF3)CF-And (CF)3)3C-. b represents an integer of 1 to 5, and b Rf groups may be the same or different from each other.
Q-Examples of the anion represented include: cl-、Br-、F-。
(BQ4)-、(SbQ6)-、(AsQ6)-、(PQ6)-Examples of the anion represented include: BF (BF) generator4 -、SbF6 -、AsF6 -、PF-。
R10SO3 -Examples of the anion represented include: CF (compact flash)3SO3 -、C2F5SO3 -、C3F7SO3 -、C4F9SO3 -、C6F5SO3 -、C3F7SO3 -P-toluenesulfonate anion, benzenesulfonate anion, camphorsulfonate anion, methanesulfonate anion, ethanesulfonate anion, propanesulfonate anion and butanesulfonate anion.
(R10SO2)3C-Examples of the anion represented include: (CF)3SO2)3C-、(C2F5SO2)3C-、(C3F7SO2)3C-And (C)4F9SO2)3C-。
(R10SO2)2N-Examples of the anion represented include: (CF)3SO2)2N-、(C2F5SO2)2N-、(C3F7SO2)2N-And (C)4F9SO2)2N-。
B(C6Q5)4 -、Ga(C6Q5)4 -Examples of the anion represented include: b (C)6F5)4 -、Ga(C6F5)4 -。
[(Rf)bPF6-b]-Examples of the anion represented include: (CF)3CF2)2PF4 -、(CF3CF2)3PF3 -、[(CF3)2CF]2PF4 -、[(CF3)2CF]3PF3 -、(CF3CF2CF2)2PF4 -、(CF3CF2CF2)3PF3 -、[(CF3)2CFCF2]2PF4 -、[(CF3)2CFCF2]3PF3 -、(CF3CF2CF2CF2)2PF4 -And (CF)3CF2CF2CF2)3PF3 -And the like.
Preparation method
The method for preparing the bis-triphenylsulfonium salt compound of the present invention is not particularly limited, and a well-known organic synthesis process can be employed. For example, the bis-triphenylsulfonium salt compound of the present invention can be obtained by subjecting a diaryl sulfoxide and a diaryl compound to a sulfonium sulfonation reaction by a production method described in patent document CN1871212A, and introducing an anion through a salt exchange reaction as needed.
Applications of
The bis-triphenylsulfonium salt compound of the present invention has a property of releasing a lewis acid by irradiation with active energy rays, and can act on an acid-reactive organic substance to decompose or polymerize, and therefore, can be used as a photoacid generator for a photoresist or a cationic polymerization photoinitiator.
As the energy ray to be used, a low-pressure, medium-pressure, high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, LED lamp, xenon lamp, carbon arc lamp, fluorescent lamp, semiconductor solid-state laser, argon laser, He-Cd laser, KrF excimer laser, ArF excimer laser or F excimer laser can be used2As the energy ray in the ultraviolet-visible light region obtained by laser or the like, a radiation having high energy such as an electron beam or an X-ray may be used.
The bis-triphenylsulfonium salt compound of the present invention can be mixed with a photosensitive active monomer (e.g., a cationically polymerizable compound) to form a photosensitive composition, and can be used in the fields of production of a lithographic printing plate, a relief printing plate, a photoresist for a printed circuit board, an IC, an LSI, a photocurable ink, a coating material, an adhesive, etc.
The bis-triphenylsulfonium salt compound shown in the general formula (I) has excellent solubility, higher light generation efficiency and photosensitive activity and good market application value.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Preparation examples
Example 1: preparation of sulfonium salt A-1
(1) Intermediate a1
110.0g of o-fluorotoluene, 59.5g of thionyl chloride and 200mL of dichloromethane are put into a 500mL four-neck flask, cooled in an ice-water bath, controlled at about 5 ℃, 66.5g of aluminum trichloride is added in batches, the addition is finished for about 1h, stirring is continued for 2h, and the liquid phase tracking reaction is carried out until the completion. The dichloromethane solution of the product was poured into 500g of ice water, stirred continuously, the dichloromethane layer was separated, washed with water, and the dichloromethane product solution was rotary evaporated to obtain 106g of a pale yellow solid, i.e., intermediate a1, yield 79.7%, HPLC purity: 98 percent.
The product structure of the intermediate is confirmed by nuclear magnetic resonance hydrogen spectrum and mass spectrum, and the specific characterization result is as follows:
1H-NMR(CDCl3，500MHz)：2.3512(6H，s)，7.2438-7.3305(6H，m)。
MS(m/Z)：267(M+H)+。
(2) intermediate b1
Adding 66.5g of intermediate a1 and 200mL of acetic anhydride into a 500mL four-neck flask, stirring in an ice-water bath, controlling the temperature to be about 0 ℃, dropwise adding 35g of concentrated sulfuric acid (mass fraction is 70%), dropwise adding the concentrated sulfuric acid for about 1h, adding 23.3g of diphenyl sulfide into the reaction system in batches after the dropwise adding is finished, continuously stirring for 12h, slowly dropwise adding 100mL of deionized ice water, extracting the solution with benzene for 2-3 times, separating out a water layer, combining the benzene layer, washing once, and combining the water layer to obtain the aqueous solution of the intermediate b 1.
(3) Target product Compound A-1
179.5g of potassium tetrakis- (pentafluorophenyl) borate solid was added to the aqueous solution of the intermediate b1 for ion exchange, deionized water was appropriately added with stirring, the target product a-1 was gradually precipitated with the dissolution of the potassium tetrakis- (pentafluorophenyl) borate solid, and filtered and dried to obtain 158g of a white solid with a yield of 62.0%, HPLC purity: 99 percent.
The structure of the target product is confirmed by a nuclear magnetic resonance hydrogen spectrum and a mass spectrum, and the specific characterization result is as follows:
1H-NMR(CDCl3，500MHz)：2.3512(12H，s)，6.8038-7.2818(20H，m)。
MS(m/Z)：684(M)+。
example 2
Referring to the preparation method of example 1, compounds a2-a25 as shown in table 1 were prepared starting from thionyl chloride and the corresponding substituted benzene.
Structure of target product and MS (m/Z) and1the H-NMR data are shown in Table 1.
TABLE 1
Evaluation of Performance
The application properties of the photoinitiators of formula (I) of the present invention were tested by formulating exemplary photocurable compositions.
1. Dissolution Performance test
The solubility of the compounds A-1 to A-25 of the present invention and the comparative compounds B-1 and B-2 in 3-ethyl-3-hydroxymethyloxetane monomer was determined as the maximum gram dissolved in 100g of solvent at 20 ℃.
The test results are shown in table 2.
2. Acid yield test
The above-mentioned compounds were prepared in the form of 0.02mmol/g acetonitrile solutions. 5.00g of the prepared acetonitrile solution was added to a petri dish having an inner diameter of 100mm, and then irradiated with an ultraviolet lamp (model FL10BL) at 0.8mw/cm2The light intensity of (1) is received in an accumulated manner at 200mj/cm2The energy of (a). The solution after exposure was titrated with 0.05N ethanolic potassium hydroxide solution using BTB as an indicator. Titrating the corresponding solution before illumination to obtain a blank value, deducting the blank value from the titration measured value, and calculating the acid yield through the following formula:
acid yield% (% acid titration-blank value) (mol)/theoretical number of moles of compound (mol) × 100%.
The test results are shown in table 2.
3. Photosensibility test
The sensitivity of the compounds of formula (I) of the present invention was tested by configuring an exemplary photoresist.
Composition of the photoresist:
wherein the content of the first and second substances,
resin A represents
The resin B is novolac resin obtained by condensing m-cresol and p-cresol at a molar ratio of 1:1 under the catalysis of formaldehyde and acid, and has a molecular weight of about 10000;
the photoinitiator was the above-mentioned compounds A-1 to A-25 or comparative example compounds B-1 and B-2.
The components are uniformly stirred according to the proportion and filtered by a membrane filter with the aperture of 1 mu m to prepare the resist composition with the solid content of 40 percent.
The resist composition was uniformly coated on a silicon wafer substrate by a spin coater, and dried to obtain a photoresist coating layer of 20 μm thickness. Prebaking at 130 ℃ for 6min, then pattern exposure (i-line) using TME-150RSC, and exposure at 75 ℃ for 5min with a hotplate. Then, developing for 5min by adopting a tetramethylammonium hydroxide solution with the mass fraction of 2.38%, cleaning by using running water, and drying by using nitrogen to obtain a 10-micron line pattern. The lowest exposure amount at which no pattern residue is visible, i.e., the lowest exposure amount required for forming a resist pattern, is measured, and a lower value indicates a higher sensitivity of the initiator.
The test results are shown in table 2.
TABLE 2
As can be seen from the test results in Table 2, the bis-triphenylsulfonium salt compound shown in the general formula (I) shows satisfactory solubility, and has excellent acid production rate and photosensitive activity, and compared with the existing improved triphenylsulfonium salts B-1 and B-2, the bis-triphenylsulfonium salt compound has obvious performance advantages and wide application prospects.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (21)
1. A bis-triphenylsulfonium salt compound has a structure shown as a general formula (I):
wherein the content of the first and second substances,
R1represents an electron withdrawing group;
R2represents an amplifying group;
R3each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R3The groups may be linked to each other to form a ring; n represents an integer of 0 to 5;
R4each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally, the carbon-carbon bond in the group may be interrupted by-O-, -S-, and R4The groups may be linked to each other to form a ring; m represents an integer of 0 to 4;
R5each independently represents hydrogen, halogen, nitro, cyano, hydroxy, acyl, acyloxy, sulfonyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, optionally the carbon-carbon bond in the group may be interrupted by-O-, -S-,and R is5The groups may be linked to each other to form a ring; p represents an integer of 0 to 4;
a and M each independently represent a linking group;
X-denotes a non-nucleophilic anion.
2. The bis-triphenylsulfonium salt compound according to claim 1, wherein: r1Selected from the group consisting of halogen, cyano, nitro, haloalkyl, acyl, acyloxy, sulfonyl.
3. The bis-triphenylsulfonium salt compound according to claim 2, wherein:
halogen is fluorine;
the alkyl moiety in haloalkyl being C1-C8Straight chain alkyl group of (1), C3-C8Branched alkyl of, or C3-C8Cycloalkyl, haloalkyl preferably being C1-C4A perfluoroalkyl group of (a);
the acyl moiety of the acyl and acyloxy groups having
In which R is6Represents hydrogen, halogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl;
the sulfonyl group is selected from methylsulfonyl, difluoromethylsulfonyl, trifluoromethanesulfonyl, phenylsulfonyl and tosyl.
4. The bis-triphenylsulfonium salt compound according to claim 1, wherein: r2Selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted aralkyl.
5. The bis-triphenylsulfonium salt compound according to claim 4, wherein:
alkyl being unsubstituted C1-C8Straight chain alkyl or C3-C8Is preferably C1-C4Linear or branched alkyl of (a);
the alkyl part of the alkoxy radical being unsubstituted C1-C8Straight chain alkyl or C3-C8Is preferably C1-C4Linear or branched alkyl of (a);
aralkyl radicals having a phenyl end group1-C8Preferably C terminated with phenyl1-C4Linear alkyl group of (1).
6. The bis-triphenylsulfonium salt compound according to claim 1, wherein: n is 0.
7. The bis-triphenylsulfonium salt compound according to claim 1, wherein: n is 2 and two R on the same phenyl ring3Each represents R1And R2R of the uppermost benzene ring1And R2The bis-triphenylsulfonium salt is symmetrical up and down, namely the bis-triphenylsulfonium salt has a structure shown in the following general formula (II):
8. the bis-triphenylsulfonium salt compound according to claim 1, wherein: r4Selected from hydrogen, nitro, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy.
9. The bis-triphenylsulfonium salt compound according to claim 1 or 8, wherein: m represents 0, 1 or 2, preferably 0 or 1.
10. The bis-triphenylsulfonium salt compound according to claim 1 or 8, wherein: m represents 1, and R4In the ortho position to the side of the A group.
11. According toThe bis-triphenylsulfonium salt compound of claim 1, wherein: r5Selected from hydrogen, nitro, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy.
12. The bis-triphenylsulfonium salt compound according to claim 1 or 11, wherein: p represents 0, 1 or 2, preferably 0 or 1.
13. The bis-triphenylsulfonium salt compound according to claim 1 or 11, wherein: p represents 1, and R5In the ortho position to the side of the A group.
14. The bis-triphenylsulfonium salt compound according to claim 1, wherein: a represents a connecting bond,＊O＊、＊S＊Alkylene or alkenylene.
15. The bis-triphenylsulfonium salt compound of claim 14, wherein: alkylene is C1-C4The straight chain alkylene group of (a), alkenylene group is-CH ═ CH-.
16. The bis-triphenylsulfonium salt compound according to claim 1, wherein: m represents null,
＊O＊、＊S＊Or
Group, wherein R7、R8、R9Each independently represents hydrogen or C1-C20Straight or branched alkyl of (2), C3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl or C4-C20An alkylcycloalkyl group of (a).
17. The bis-triphenylsulfonium salt compound of claim 16, wherein: m is not null, A is a bond.
18. The bis-triphenylsulfonium salt compound according to claim 1, wherein: on the middle two phenyl rings, the linking position of the S atom is para to the group A.
19. Use of the bis-triphenylsulfonium salt compound as claimed in any of claims 1 to 18 as a photoacid generator for a photoresist or as a cationic polymerization photoinitiator.
20. A photosensitive composition comprising the bis-triphenylsulfonium salt compound as described in any one of claims 1 to 18.
21. Use of the photosensitive composition of claim 20 for producing lithographic and relief printing plates, printing substrates, photoresists, photocurable inks, coatings, adhesives.
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| CN201811171951.XA CN111018763B (en) | 2018-10-09 | 2018-10-09 | Bis-triphenyl sulfonium salt compound and application thereof |
| EP23154959.3A EP4198019A1 (en) | 2018-10-09 | 2019-09-27 | Triphenylphosphonium salt compound, and uses thereof |
| US17/284,274 US11746085B2 (en) | 2018-10-09 | 2019-09-27 | Triphenylsulfonium salt compound, and uses thereof |
| PCT/CN2019/108369 WO2020073822A1 (en) | 2018-10-09 | 2019-09-27 | Triphenylphosphonium salt compound, and uses thereof |
| EP19871797.7A EP3865473A4 (en) | 2018-10-09 | 2019-09-27 | Triphenylphosphonium salt compound, and uses thereof |
| KR1020217013626A KR102636084B1 (en) | 2018-10-09 | 2019-09-27 | Triphenylsulfonium salt compounds and their applications |
| JP2021519803A JP7345544B2 (en) | 2018-10-09 | 2019-09-27 | Triphenylsulfonium salt compounds and their uses |
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| CN111694215A (en) * | 2019-03-14 | 2020-09-22 | 常州强力先端电子材料有限公司 | Photoresist composition and method for forming photolithographic pattern |
| CN113336686A (en) * | 2021-05-20 | 2021-09-03 | 泰兴先先化工有限公司 | Synthetic method of mixed sulfonium salt |
| CN113801042A (en) * | 2021-08-25 | 2021-12-17 | 上海新阳半导体材料股份有限公司 | Multi-onium salt type photoacid generator for dry-method ArF light source photoetching |
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